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DOE OSTI2025

Greenhouse gas flux response in biochar- and compost-amended urban soils under simulated soil hydrologic dynamics

Understanding greenhouse gas emission dynamics in lawn soils is essential for improving climate change mitigation strategies in urban and suburban environments. This project measured fluxes of carbon dioxide (CO 2 ), methane (CH 4 ), and nitrous oxide (N 2 O) fluxes from turfgrass soil columns amended with biochar, compost, biochar-compost blend, control (no amendment) in a controlled greenhouse mesocosm experiment. This project simulated contrasting water saturation regimes consisting of normal irrigation with sprinkler, transient half or full saturation by water table manipulation, and subsequent drying phase under both sod or seeded grass conditions. Compost-amended columns (compost or biochar-compost blend) exhibited higher average CO 2 fluxes (6 µmol m-2 s-1) compared to biochar or control columns (4.5 – 5.0 µmol m-2 s-1) across all saturation levels under sod conditions. Seeded grass conditions generally resulted in less CO 2 emissions. The CO 2 fluxes were positively correlated with air temperature and negatively correlated with soil moisture. Biochar-amended columns retained high soil moisture (~95 %) throughout experiments, demonstrating superior moisture retention compared to compost. CH 4 and N 2 O fluxes exhibited temporal increases (5-8 nmol m-2 s-1) during saturation and drainage phases, indicating their sensitivity to hydrologic conditions. These findings suggest that temperature and amendment types are primary driver of CO 2 emissions, while CH 4 and N 2 O fluxes are more responsive to water saturation dynamics in lawn soils.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1997

Application of Multitemporal Remotely Sensed Soil Moisture for the Estimation of Soil Physical Properties

This paper demonstrates the use of multitemporal soil moisture derived from microwave remote sensing to estimate soil physical properties. The passive microwave ESTAR instrument was employed during June 10-18, 1992, to obtain brightness temperature (TB) and surface soil moisture data in the Little Washita watershed, Oklahoma. Analyses of spatial and temporal variations of TB and soil moisture during the dry-down period revealed a direct relationship between changes in T and soil moisture and soil physical (viz. texture) and hydraulic (viz. saturated hydraulic conductivity, K(sat)) properties. Statistically significant regression relationships were developed for the ratio of percent sand to percent clay (RSC) and K(sat), in terms of change components of TB and surface soil moisture. Validation of results using field measured values and soil texture map indicated that both RSC and K(sat) can be estimated with reasonable accuracy. These findings have potential applications of microwave remote sensing to obtain quick estimates of the spatial distributions of K(sat), over large areas for input parameterization of hydrologic models.

Mattikalli, N. M.↗

DOE OSTI2021

Data from: "Warming of alpine tundra enhances belowground production and shifts community towards resource acquisition traits"

This archive contains data used to draw conclusions in “Warming of alpine tundra enhances belowground production and shifts community towards resource acquisition traits”, by Yang et al. 2020. Data were collected on Niwot Ridge, in an alpine meadow within the Alpine Treeline Warming Experiment (ATWE) field sites in Colorado, USA. Samples were also processed in the U.S. Geological Survey Forest and Rangeland Ecosystem Science Center, in Boise, Idaho. File formats in this archive include comma-separated values (.csv), portable document format (.pdf), Microsoft Excel (.xlsx), and two types of geospatial files: keyhole markup language (.kml), and ESRI shapefiles (.shp). Leaf scans are .jpg images, and root scans are .tiff/.tif images.The .csv files can be opened using R, Microsoft Excel, or any simple text-editing software such as TextEdit and Notepad. Microsoft Excel files can be opened using Microsoft Excel, and .pdf files can be opened with Adobe Acrobat Reader, Preview, or other compatible programs. Scanned images can be opened using any photo and/or picture viewing software.The .kml file can be opened using Google Earth and Google Maps, and the shapefiles can be opened by any programs compatible with shapefiles, such as the ArcGIS Desktop suite, and QGIS.------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------Measures of belowground net primary productivity (BNPP) are required to understand whether aboveground net primary production (ANPP) changes reflect changes in allocation or are indicative of a whole plant NPP response. Plant functional traits provide a key way to scale from the individual plant to the community level, and provide insight into drivers of NPP responses to environmental change. We used infrared heaters to warm an alpine plant community at Niwot Ridge, Colorado, and applied supplemental water to compensate for soil water loss induced by warming. We measured ANPP, BNPP, and leaf and root functional traits across treatments after 5 years of continuous warming. Community-level ANPP and total NPP (ANPP + BNPP) did not respond to heating or watering, but BNPP increased in response to heating. Heating decreased community-level leaf dry matter content and increased total root length, indicating a shift in strategy from resource conservation to acquisition in response to warming.

13C/12C isotope ratio↗

NASA NTRS2001

Carbon Storage in Wetlands and Lakes of the Eastern US

Carbon stored underground may participate in a positive feedback with climate warming, as higher temperatures accelerate decomposition reactions and hence CO2 release. Assessing how below-ground carbon storage varies with modern climate and paleoclimate will advance understanding of this feedback in two ways. First, it will estimate the sensitivity of carbon storage to temperature and precipitation changes. Second, it will help quantify the size of carbon stocks available for the feedback, by indicating how current regional climate differences affect carbon storage. Whereas many studies of below-ground carbon storage concentrate on soils, this investigation focuses on the saturated and primarily organic material stored in wetlands and lake sediments. This study surveys research done on organic sediment depth and organic content at 50-100 sites in the eastern U.S., integrating our own research with the work of others. Storage depth is evaluated for sediments from the past 10,000 years, a date reflected in pollen profiles. Organic content is measured chiefly by loss-on-ignition (101). These variables are compared to characteristics of the sites such as latitude, altitude, and vegetation as well as local climate. Preliminary results suggest a strong relationship between latitude and depth of organic material stored over the last 10,000 years, with more accumulation in the northeastern US than the southeastern US. Linking the percent organic matter to actual carbon content is in progress with wetlands from Black Rock Forest and Alpine Swamp.

Renik, Byrdie↗

DOE OSTI2025

CMP Pits and D-Area Watershed Infiltrometer Testing

Savannah River National Laboratory (SRNL) conducted saturated hydraulic conductivity field testing at the Chemical, Metals, and Pesticide Pits (CMP Pits) and the D-Area watershed to develop infiltration rates for use in future updates to the CMP Pits groundwater flow model. Approximately 18 testing locations were selected at each site based on the soil series that were identified in the Soil Survey of Savannah River Plant Area, Parts of Aiken, Barnwell, and Allendale Counties, South Carolina.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2025

CMP Pits and D-Area Watershed Infiltrometer Testing

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS2000

BOREAS HYD-1 Soil Hydraulic Properties

The Boreal Ecosystem-Atmosphere Study (BOREAS) Hydrology (HYD)-1 team coordinated a program of data collection to measure and monitor soil properties in collaboration with other science team measurement needs. This data set contains soil hydraulic properties determined at the Northern Study Area (NSA) and Southern Study Area (SSA) flux tower sites based on analysis of in situ tension infiltrometer tests and laboratory-determined water retention from soil cores collected during the 1994-95 field campaigns. Results from this analysis are saturated hydraulic conductivity, and fitting parameters for the van Genuchten-Mualem soil hydraulic conductivity and water retention function at flux tower sites. The data are contained in tabular ASCII files. The HYD-01 soil hydraulic properties data are available from the Earth Observing System Data and Information System (EOSDIS) Oak Ridge National Laboratory (ORNL) Distributed Active Archive Center (DAAC). The data files are available on a CD-ROM (see document number 20010000884).

Hall, Forrest G.↗

DOE OSTI2023

Impact of biochar amendments on soil water and plant uptake dynamics under different cropping systems

Abstract Application of biochar amendments in agricultural systems has received much attention in recent years. In this study, we assess the 5‐year impacts of biochar application on soil water and plant interactions for an irrigated fresh market tomato ( Solanum lycopersicum ) and a rainfed pasture ( Poaceae ) cropping system. In particular, we focus on three varieties of locally produced biochar from agricultural waste materials—almond shell, walnut shell, and almond pruning residues that are pyrolyzed using a mobile pyrolysis unit. We used the soil hydrological model HYDRUS‐1D to explicitly track seasonal and annual soil water fluxes through changes in water retention, drainage, evaporation, and plant water uptake under biochar application. Modeling results show that the application of biochar at 5% increased soil water availability within the top 20 cm for a rainfed system, irrespective of biochar amendment type. This is clearly indicative of higher plant water uptake and greater water use efficiency (WUE) under biochar application. In contrast, a similar biochar amendment for the irrigated system did not affect WUE, instead reducing seasonal soil evaporation loss and thereby reducing irrigation demand. In both cropping systems, year‐to‐year variability in precipitation significantly impacted the total amount of water saved under biochar application with certain amendments retaining more water than others. Given that biochar application increased water retention irrespective of cropping systems, we further used a simple approach to determine yield trade‐off, if any, between control and biochar treatments. Our economic balance clearly demonstrates that the water saved by amending soil with biochar does not offset the yield disparity if compensated with carbon credits and therefore, application of biochar should be actively considered for both its direct and indirect benefits to potential greenhouse gas mitigation (e.g., diverting orchard waste from open burning), water savings, and soil health.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1999

Calcium Solubility and Cation Exchange Properties in Zeoponic Soil

An important aspect of a regenerative life support system at a Lunar or Martian outpost is the ability to produce food. Essential plant nutrients, as well as a solid support substrate, can be provided by: (1) treated Lunar or Martian regolith; (2) a synthetic soil or (3) some combination of both. A synthetic soil composed of ammonium- and potassium-saturated chinoptlolite (a zeolite mineral) and apatite, can provide slow-release fertilization of plants via dissolution and ion-exchange reactions. Previous equilibrium studies (Beiersdorfer, 1997) on mixtures of synthetic hydroxyapatite and saturated-clinoptilolite indicate that the concentrations of macro-nutrients such as ammonium, phosphorous, potassium, magnesium, and calcium are a function of the ratio of chinoptilolite to apatite in the sample and to the ratio of potassium to ammonium on the exchange sites in the clinoptilolite. Potassium, ammonium, phosphorous, and magnesium are available to plants at sufficient levels. However, calcium is deficient, due to the high degree of calcium adsorption by the clinoptilolite. Based on a series of batch-equilibration experiments, this calcium deficiency can be reduced by (1) treating the clinoptilolite with CaNO3 or (2) adding a second Ca-bearing mineral (calcite, dolomite or wollastonite) to the soil. Treating the Cp with CaNO3 results in increased Ca in solution, decreased P in solution and decreased NH4 in solution. Concentrations of K were not effected by the CaNO3 treatment. Additions of Cal, Dol and Wol changed the concentrations of Ca and P in solution in a systematic fashion. Cal has the greatest effect, Dol the least and Wol is intermediate. The changes are consistent with changes expected for a common ion effect with Ca. Higher concentrations of Ca in solution with added Cal, Dol or Wol do not result in changes in K or NH4 concentrations.

Beiersdorfer, Raymond E.↗

DOE OSTI2020

Quantifying cover crop effects on soil health and productivity

The dataset presented here supports the research paper entitled “A calculator to quantify cover crop effects on soil health and productivity”. Soil health (sometimes used synonymously with soil quality) is a concept that describes soil as a living system to sustain plants, animals, and human. Soil physical, chemical, and biological properties, along with their interactions, are required to quantify soil health. The use of cover crops in agricultural rotations may enhance soil health, yet there has been little progress in understanding how external factors such as climate, soil type, and agronomic practices affect soil and cash crop responses. In response, this dataset compiles measurements from 281 studies and provides an analysis of field-measured changes in 38 soil health indicators due to cover crop usage. Environmental and background indicators were also compiled to assess how climatic and management practices affect soil and cash crop responses to cover crops, with specific categories including climate type (tropical, arid, temperate, and continental), soil texture (coarse, medium, and fine), cover crop type (legume, grass, multi-species mixture, and other), and cash crop type (corn, soybean, wheat, vegetable, corn-soybean rotation, corn-soybean-wheat rotation, and other). An unbalanced analysis of variation was used to determine the hierarchy of most to least important factors that affected responsiveness of each soil health indicator. Based on the hierarchy structure, a soil health calculator was then developed to quantify the response of 13 parameters – erosion, runoff, weed suppression, soil aggregate stability, leaching, infiltration, microbial biomass carbon, soil bulk density, soil organic carbon, soil nitrogen, microbial biomass nitrogen, cash crop yield, and saturated hydraulic conductivity – to cover crops. The presented data in the calculator report the mean change in parameter values based on all combinations of climate, soil texture, cover crop type, and cash crop type.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS2015

Variability of Phenology and Fluxes of Water and Carbon with Observed and Simulated Soil Moisture in the Ent Terrestrial Biosphere Model (Ent TBM Version 1.0.1.0.0)

The Ent Terrestrial Biosphere Model (Ent TBM) is a mixed-canopy dynamic global vegetation model developed specifically for coupling with land surface hydrology and general circulation models (GCMs). This study describes the leaf phenology submodel implemented in the Ent TBM version 1.0.1.0.0 coupled to the carbon allocation scheme of the Ecosystem Demography (ED) model. The phenology submodel adopts a combination of responses to temperature (growing degree days and frost hardening), soil moisture (linearity of stress with relative saturation) and radiation (light length). Growth of leaves, sapwood, fine roots, stem wood and coarse roots is updated on a daily basis. We evaluate the performance in reproducing observed leaf seasonal growth as well as water and carbon fluxes for four plant functional types at five Fluxnet sites, with both observed and prognostic hydrology, and observed and prognostic seasonal leaf area index. The phenology submodel is able to capture the timing and magnitude of leaf-out and senescence for temperate broadleaf deciduous forest (Harvard Forest and Morgan- Monroe State Forest, US), C3 annual grassland (Vaira Ranch, US) and California oak savanna (Tonzi Ranch, US). For evergreen needleleaf forest (Hyytiäla, Finland), the phenology submodel captures the effect of frost hardening of photosynthetic capacity on seasonal fluxes and leaf area. We address the importance of customizing parameter sets of vegetation soil moisture stress response to the particular land surface hydrology scheme. We identify model deficiencies that reveal important dynamics and parameter needs.

Soil moisture↗

DOE OSTI2024

Belowground plant allocation regulates rice methane emissions from degraded peat soils

Carbon-rich peat soils have been drained and used extensively for agriculture throughout human history, leading to significant losses of their soil carbon. One solution for rewetting degraded peat is wet crop cultivation. Crops such as rice, which can grow in water-saturated conditions, could enable agricultural production to be maintained whilst reducing CO 2 and N 2 O emissions from peat. However, wet rice cultivation can release considerable methane (CH 4 ). Water table and soil management strategies may enhance rice yield and minimize CH 4 emissions, but they also influence plant biomass allocation strategies. It remains unclear how water and soil management influences rice allocation strategies and how changing plant allocation and associated traits, particularly belowground, influence CH 4 -related processes. We examined belowground biomass (BGB), aboveground biomass (AGB), belowground:aboveground ratio (BGB:ABG), and a range of root traits (root length, root diameter, root volume, root area, and specific root length) under different soil and water treatments; and evaluated plant trait linkages to CH 4 . Rice (Oryza sativa L.) was grown for six months in field mesocosms under high (saturated) or low water table treatments, and in either degraded peat soil or degraded peat covered with mineral soil. We found that BGB and BGB:AGB were lowest in water saturated conditions where mineral soil had been added to the peat, and highest in low-water table peat soils. Furthermore, CH 4 and BGB were positively related, with BGB explaining 60% of the variation in CH 4 but only under low water table conditions. Our results suggest that a mix of low water table and mineral soil addition could minimize belowground plant allocation in rice, which could further lower CH 4 likely because root-derived carbon is a key substrate for methanogenesis. Minimizing root allocation, in conjunction with water and soil management, could be explored as a strategy for lowering CH 4 emissions from wet rice cultivation in degraded peatlands.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2020

Evaluating integrated surface/subsurface permafrost thermal hydrology models in ATS (v0.88) against observations from a polygonal tundra site

Numerical simulations are essential tools for understanding the complex hydrologic response of Arctic regions to a warming climate. However, strong coupling among thermal and hydrological processes on the surface and in the subsurface and the significant role that subtle variations in surface topography have in regulating flow direction and surface storage lead to significant uncertainties. Careful model evaluation against field observations is thus important to build confidence.We evaluate the integrated surface/subsurface permafrost thermal hydrology models in the Advanced Terrestrial Simulator (ATS) against field observations from polygonal tundra at the Barrow Environmental Observatory. ATS couples a multiphase, 3D representation of subsurface thermal hydrology with representations of overland nonisothermal flows, snow processes, and surface energy balance. We simulated thermal hydrology of a 3D ice-wedge polygon with geometry that is abstracted but broadly consistent with the surface microtopography at our study site. The simulations were forced by meteorological data and observed water table elevations in ice-wedge polygon troughs. With limited calibration of parameters appearing in the soil evaporation model, the 3-year simulations agreed reasonably well with snow depth, summer water table elevations in the polygon center, and high-frequency soil temperature measurements at several depths in the trough, rim, and center of the polygon. Upscaled evaporation is in good agreement with flux tower observations. The simulations were found to be sensitive to parameters in the bare soil evaporation model, snowpack, and the lateral saturated hydraulic conductivity.Timing of fall freeze-up was found to be sensitive to initial snow density, illustrating the importance of including snow aging effects. The study provides new support for an emerging class of integrated surface/subsurface permafrost simulators.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2025

A statistical and simulation-informed model for estimating permeability from pore size distribution in saturated geomaterials

Accurate permeability estimation is essential across subsurface engineering applications but remains challenging due to the complex pore structures of natural geomaterials. Traditional empirical methods and simplified theoretical models often inadequately capture the role of pore size distribution and connectivity. Here, this study develops a statistical and simulation-informed permeability model that collapses pore-scale complexity into a compact scaling of the form k = αϕμ d 2 , where ϕ is porosity, μ d is mean pore size, and α is a weakly varying coefficient. By combining pore network simulations with statistical analysis of unimodal and bimodal pore size distributions, we identify three key findings: (i) permeability is much more sensitive to mean pore size than to porosity; (ii) across extensive datasets, the ratio σ d /μ d (standard deviation to mean) clusters around a characteristic value ∼0.4, allowing the effects of the full pore size distribution to be represented by μ d and a narrowly varying α ≈ 0.05; and (iii) for bimodal systems, there exists a critical fraction of small pores ∼0.78 above which flow becomes small-pore dominated, enabling the definition of an effective flow-controlling pore population and facilitating simplified permeability estimation for such systems. The resulting model, which requires only porosity and a representative mean pore size as inputs, is validated against comprehensive experimental datasets (>1700 samples) spanning diverse soils and rocks and achieves good predictive accuracy. Overall, this work provides a physically grounded yet practically simple permeability estimator suitable for subsurface engineering, environmental protection, and resource management applications.

Permeability↗

DOE OSTI2024

Data for: Time to anoxia: Observations and predictions of oxygen drawdown following coastal flood events

This dataset contains data and code associated with the paper Patel et al. "Time to anoxia: Observations and predictions of oxygen drawdown following coastal flood events".The coastal terrestrial-aquatic interface (TAI) is a highly dynamic system characterized by strong physical, chemical, and biological gradients. In particular, shifting soil redox conditions and consumption of terminal electron acceptors, due in part to dynamic hydrologic conditions, is a strong driver of carbon availability and transformations across TAIs. However, while redox dynamics are well described, our ability to quantitatively forecast rates of oxic to anoxic shifts in soils with different characteristics and inundation regimes is limited. We integrated field measurements, laboratory incubations, and model simulations to improve mechanistic understanding of oxygen consumption dynamics in coastal soils. Continuous in situ monitoring unexpectedly revealed that flooding caused temporary spikes in subsurface dissolved oxygen followed by rapid consumption in the wetlands. To further investigate these mechanisms in a controlled setting, we performed laboratory incubations using surface and subsurface soils from a TAI gradient (defined here as upland forest to transitional forest to wetland) in Western Lake Erie to measure oxygen consumption rates in TAI soils during flood events. In our experiments, wetland soils reached anoxia the fastest, in ∼ 9 h on average, whereas upland soils turned anoxic in ∼ 18 h. Subsurface upland soils did not turn anoxic even after two weeks of saturation in the lab, and their oxygen consumption patterns suggested carbon and/or nutrient limitation. These results are consistent with in-situ groundwater redox and oxygen measurements in the field, where wetland soils exhibited the highest rates of oxygen consumption along the TAI. Model simulations of oxygen consumption suggested that oxygen consumption had stronger abiotic controls in wetland soils but stronger biotic controls in upland soils, providing a useful framework for future incubation experiments. Microbial activity is a strong driver of oxygen consumption in TAI soils, although it is constrained by the availability of dissolved carbon in subsurface soils.This dataset contains a compressed (.zip) archive of the data and R scripts used for this manuscript. The dataset includes files in .csv format, which can be accessed and processed using MS Excel or R. This archive can also be accessed on GitHub at https://github.com/COMPASS-DOE/cmps-time_to_anoxia (DOI: 10.5281/zenodo.10815374).

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1992

Sulfate reduction and other sedimentary biogeochemistry in a northern New England salt marsh

Sulfate reduction rates, dissolved iron and sulfide concentrations, and titration alkalinity were measured in salt marsh soils along a transect that included areas inhabited by both the tall and short forms of Spartina alterniflora and by Spartina patens. Pore waters were collected with in situ 'sippers' to acquire temporal data from the same location without disturbing plant roots. During 1984, data collected at weekly intervals showed rapid temporal changes in belowground biogeochemical processes that coincided with changes in S. alterniflora physiology. Rates of SO4(-2) reduction increased fivefold (to greater than 2.5 micromol ml(sup -1)d(sup -1)) when plants began elongating aboveground yet decreased fourfold upon plant flowering. This rapid increase in rates of SO4(-2) reduction must have been fueled by dissolved organic matter released from roots only during active growth. Once plants flowered, the supply of oxidants to the soil decreased and sulfide and alkalinity concentrations increased despite decreases in SO4(-2) reduction and increases in SO4(-2):Cl(-) ratios. Sulfide concentrations were highest in soils inhabited by tallest plants. During 1985, S. alterniflora became infested with fly larvae (Chaetopsis apicalis John) and aboveground growth ceased in late June. This cessation was accompanied by decreased rates of SO4(-2) reduction similar to those noted during the previous year when flowering occurred. After the fly infestation, the pore-water chemical profiles of these soils resembled profiles of soils inhabited by the short form of S. alterniflora. The SO4(-2) reduction rates in S. patens soils are the first reported. Rates were similar to those in S. alterniflora except that they did not increase greatly when S. patens was elongating. Tidal and rainfall events produced desiccation-saturation cycles that altered redox conditions in the S. patens soils, resulting in rapid changes in the dissolution and precipitation of iron and in the magnitude and spatial distribution of SO4(-2) reduction.

Hines, Mark E.↗

NASA NTRS1985

Rn-222 tracing and stable isotope measurements of biogenic gas fluxes from methane saturated sediments

Transport of reduced biogenic gases from anoxic sediments and soils to the atmosphere can be quantitatively studied through measurement of radon-222/radium-226 disequilibrium. In previous work, seasonal variations in biogenic gas transport mechanisms, net fluxes and overall composition were documented. Now presented are direct field measurements of radon-222 activity in gases exiting organic rich sediments which show their usefulness for tracing of the stripping of dissolved biogenic gases from within the sediment column and transport via bubble ebullition. Methane is depleted in deuterium during the summer as compared with winter months and is in general lighter than in most marine sediments signaling the probable importance of acetate as an important precursor molecule. The significant seasonal isotopic variations observed illustrate the importance of understanding mechanisms and rates of biogenic gas production in order to interpret observed tropospheric isotopic data.

Martens, Christopher S.↗

DOE OSTI2022

Sulfur Biogeochemical Cycling and Redox Dynamics in a Shale-Dominated Mountainous Watershed

Sulfur (S) is an essential macronutrient and important component of the earth’s crust, and its cycling has critical impacts on trace metal mobility, water quality, and human health. Pyrite weathering is the primary pathway by which sulfur enters surface waters. However, biogeochemical cycling of sulfur in soils and the river corridor mediates sulfate exports. In this study, we identified the major forms of sulfur across multiple compartments and scales in a pristine mountainous watershed, including shale bedrock weathering profiles, hillslope soils, and alluvial floodplain sediments, in order to provide insight into biogeochemical sulfur cycling in a hydrologically variable alpine system. X-ray absorption near-edge spectroscopy (XANES) analysis of shale weathering profiles showed clear evidence of pyrite oxidation to sulfate, with large accumulations of intermediate S(0) (20%–53%). Micro-scale XANES showed evidence of reprecipitation of pyrite at fracture surfaces within the permanently saturated zone. Organic sulfur dominated S speciation in shallow hillslope soil and floodplain sediment, with little evidence of reduced inorganic S. However, mackinawite formation, representing active sulfate reduction, was observed in saturated oxbow sediments and saturated weathered shale underlying floodplain sediments. Further evidence of sulfate reduction from aqueous sulfur isotopic analysis was observed in shallow groundwater transects across an Fe-reducing meander, whereas increases in pore water sulfate concentrations implied sulfur oxidation at other locations. Furthermore, the data present an integrated picture of sulfur cycling in a shale-dominated watershed, where riverine sulfate exports are mediated by biological cycling, particularly in redox-stratified and temporally dynamic hyporheic zone sediments.

58 GEOSCIENCES↗