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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

A Flux Detection Probe to Quantify Dynamic Groundwater-Surface Water Exchange in the Hyporheic Zone

A new probe was designed to quantify groundwater-surface water exchange in the hyporheic zone under dynamic stage condition. Current methods focus on either vertical pore water velocity or Darcy flux measurements. Both parameters must be understood to evaluate residence time and mass flux of constituents. Furthermore, most instruments are not well suited for monitoring instantaneous velocity or flux under dynamic exchange conditions. For this reason, the flux detection probe (FDP) was designed that employs electrogeophysical measurements to estimate in situ sediment porosity, which can be used to convert pore water velocity to Darcy flux. Dynamic pore water velocity is obtained by monitoring fluid conductivity and temperature along the FDP probe. Pressure sensors deployed at the top and bottom of the probe provide the additional information necessary to estimate vertical permeability. This study focuses on the use of a geophysical method to estimate pore water velocity, porosity, and permeability within a controlled soil column where simulated river water displaces simulated groundwater. The difference between probe derived and theoretical pore water velocity using natural tracers such as electrical conductivity and temperature was -4.9 and 3.9% for downward flow and 1.1 and 12.8% for upward flow, respectively. The difference in porosity calculated from mass and volume packed in the soil column and probe measure porosity ranged between -3.2% and 1.5%. Also, the calculated hydraulic conductivity differed from probe derived values by -8.9%.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

High methane concentrations in tidal salt marsh soils: Where does the methane go?

Abstract Tidal salt marshes produce and emit CH 4 . Therefore, it is critical to understand the biogeochemical controls that regulate CH 4 spatial and temporal dynamics in wetlands. The prevailing paradigm assumes that acetoclastic methanogenesis is the dominant pathway for CH 4 production, and higher salinity concentrations inhibit CH 4 production in salt marshes. Recent evidence shows that CH 4 is produced within salt marshes via methylotrophic methanogenesis, a process not inhibited by sulfate reduction. To further explore this conundrum, we performed measurements of soil–atmosphere CH 4 and CO 2 fluxes coupled with depth profiles of soil CH 4 and CO 2 pore water gas concentrations, stable and radioisotopes, pore water chemistry, and microbial community composition to assess CH 4 production and fate within a temperate tidal salt marsh. We found unexpectedly high CH 4 concentrations up to 145,000 μmol mol −1 positively correlated with S 2− (salinity range: 6.6–14.5 ppt). Despite large CH 4 production within the soil, soil–atmosphere CH 4 fluxes were low but with higher emissions and extreme variability during plant senescence (84.3 ± 684.4 nmol m −2 s −1 ). CH 4 and CO 2 within the soil pore water were produced from young carbon, with most Δ 14 C‐CH 4 and Δ 14 C‐CO 2 values at or above modern. We found evidence that CH 4 within soils was produced by methylotrophic and hydrogenotrophic methanogenesis. Several pathways exist after CH 4 is produced, including diffusion into the atmosphere, CH 4 oxidation, and lateral export to adjacent tidal creeks; the latter being the most likely dominant flux. Our findings demonstrate that CH 4 production and fluxes are biogeochemically heterogeneous, with multiple processes and pathways that can co‐occur and vary in importance over the year. This study highlights the potential for high CH 4 production, the need to understand the underlying biogeochemical controls, and the challenges of evaluating CH 4 budgets and blue carbon in salt marshes.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Colloidal metal transport in soils developing on historic coal mine spoil

Chemical weathering of pyrite via oxidative dissolution is well-known for generating Fe(III)-bearing colloids at acid mine drainage (AMD) sites; however, the potential for physical weathering of pyrite-bearing materials and subsequent release and transport of colloidal pyrite and associated trace metals has not been studied. Here, we monitored the colloidal metal transport in soil developing on abandoned coal mine spoil with a history of AMD generation to systematically study the contribution of colloids to base and trace metal transport and determine the elemental and mineralogical composition of colloids. Additionally, we collected soil pore water using lysimeters with a pore size of approximately 1.3 μm and centrifugation was used to separate the colloids from aqueous fractions. Metal concentrations of Na, Ca, Mg, K, Si, Al, Mn, Fe, Cu, and Zn were analyzed. Our results show only 14% of the total Al and Cu were present in colloidal fractions whereas 23%, 43%, and 54% of Fe, Mn, and Zn were transported in the colloidal phase, respectively. In contrast, all base metals were primarily present in the aqueous concentration with a small fraction (<10%) present in the colloidal phase. The colloidal fractions of the base metals were inferred to be associated with the concentration of clay colloids. The release of colloids exhibited possible sensitivity toward weather conditions such as alternating high temperatures and rainfall during summer (May–July) compared to fall (August–November). The morphology, elemental, and mineral composition of colloids were determined by a scanning electron microscopy equipped with energy dispersive spectroscopy (SEM-EDS) and X-ray diffraction (XRD). Colloids were dominated by phyllosilicates (biotite, muscovite, and kaolinite) with minor quartz and feldspars. Other minerals phases identified in colloidal fractions were hematite, goethite, arsenopyrite, and chalcopyrite. Colloids consisting of Fe, S, and O with structures resembling framboidal pyrite were identified, which is consistent with the non-silicates minerals identified by XRD. Our study suggests that the physical weathering of pyrite in the mine spoil can generate colloidal pyrite, which is mobilized and transported by soil pore water. Our results also indicate that these pyritic colloids are associated with toxic trace metals including Cu, Mn, and Zn. Colloid mobilization is also impacted by changes in temperature and precipitation, where clay mobilization afer rain events is favored. Further, sudden spikes in aqueous and/or colloidal concentrations may be the result of local heterogeneity within soils developing on mine spoil, indicating that further field-based work is necessary to better characterize pore-scale processes that control aqueous and colloid transport at similar sites to have a better understanding of potential contaminant transport from mine spoil systems.

58 GEOSCIENCES↗
DOE OSTI2024

Characterization of Nitrate, Nitrite, Ammonia, and Tritium in D0220 Cores

This report describes characterization of nitrogen species (nitrate, nitrite, ammonia) in aqueous and solid phases in cores taken in borehole D0220 (well 299-E25-245) under crib 216-A-37-1 at the Hanford Site in 2022 to evaluate (a) the types of nitrogen species currently in the vadose zone and (b) the migration of nitrogen species in the vadose zone. Ammonia and tritium from PUREX decladding condensate were sporadically discharged to the crib from 1977 to 1989. During discharge operations, the estimated travel time through the vadose zone to groundwater was 2.5 to 9 months. By 2003, a characterization borehole (C4106) showed residual pore water with elevated tritium and nitrate in the first 100 ft of the vadose zone, which is likely from the crib. However, there was significantly more nitrate present at the shallowest depth (15 to 22 ft), which may indicate a different source for nitrate, such as adsorbed ammonia slowly being oxidized or nitrogen species precipitates slowly dissolving. In this study, more extensive nitrogen species characterization was done on D0220 cores (drilled in 2022) at 40- and 262-ft depths, which included (a) aqueous nitrate, nitrite, and tritium; (b) adsorbed ammonia; (c) nitrogen in carbonates (or other minerals dissolved in acidic acid); (d) nitrogen in iron oxides (or other minerals dissolved in oxalic acid); and (e) nitrogen in hard-to-extract minerals (minerals dissolved in nitric acid). High pore water nitrate (226 to 331 mg/L) at 40-ft depth measured in D0220 (2022) compared to 60 mg/L at 40-ft depth in C4106 (2003) may indicate nitrate is migrating deeper. Tritium concentrations (pore water 132,000 to 148,000 pCi/L) measured in D0220 at 40-ft depth in 2022 were considerably higher than in C4106 at 40-ft depth (160 pCi/L). Additional nitrogen species mass was present in adsorbed and precipitated phases in D0220 cores. Low adsorbed ammonia was measured at 40.1- and 261.7-ft depths. Low concentrations of carbonate associated nitrogen and iron oxide-associated nitrogen were present at 40.1 and 40.6 ft depths. Nitrogen species in solid phase extractions indicate nitrogen precipitates or aqueous nitrate or ammonia trapped in sediment microfractures that are coated by precipitates. Overall, the nitrogen species and tritium characterization at two depths in D0220 showed that additional nitrogen species were present in the vadose zone. In addition, elevated pore water nitrate in D0220 at 40 ft depth from 2022 may indicate vertical migration compared to C4106 nitrate profile from 2003. Analysis of additional depths in D0220 and spatial variability of the nitrate plume along the length of the crib (from surface electrical resistivity) would be extremely useful for this comparison.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

High nitrate variability on an Alaskan permafrost hillslope dominated by alder shrubs

Abstract. In Arctic ecosystems, increasing temperatures are driving the expansion of nitrogen (N) fixing shrubs across tundra landscapes. The implications of this expansion to the biogeochemistry of Arctic ecosystems are of critical importance and more work is needed to better understand the form, availability, and transportation potential of N from these shrubs across a variety of Arctic landscapes. To gain insights into the processes controlling N within a permafrost hillslope system, the spatiotemporal variability of nitrate (NO3-) and its environmental controls were investigated at an alder (Alnus viridis spp. fruticosa) dominated permafrost tundra landscape in the Seward Peninsula, Alaska, USA. Soil pore water was collected from locations within alder shrubland growing along a well-drained hillslope and was compared to soil pore water collected from locations outside (upslope, downslope, and between) the alder shrubland. Soil pore water collected within alder shrubland had an average NO3-N (nitrogen from nitrate) concentration of 4.27±8.02 mg L−1 and differed significantly from locations outside alder shrubland (0.23±0.83 mg L−1; p<0.05). Temporal variation in NO3-N within and downslope of alder shrubland co-occurred with precipitation events where NO3- that accumulated in the soil was likely flushed downslope during rainfall. These findings have important implications for nutrient availability and mobility in N-limited permafrost systems that are experiencing shrub expansion in response to a warming Arctic.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Hyporheic, Floodplain, and Surface Water (on Floodplain and River) Geochemical Datasets, and Shapefiles on Meander C at the East River, Colorado

The purpose of this dataset was to sample surface water and groundwater geochemistry at random locations in the East River, Colorado to provide a broad spatial dataset of geochemistry. The East River is part of the Watershed Function Scientific Focus Area (WFSFA) located in the Upper Colorado River Basin, United States. We conducted this random sampling at multiple time points including during the snowmelt flooding stage, during peak flood, during the falling limb of flood, and during baseflow. This datasets contain many datafiles. We include flat text files of surface water geochemistry including surface water on the floodplain and surface water in the river, geochemistry of floodplain pore-water samples, and geochemistry of hyporheic pore-water samples. All datasets are also included as shapefiles so location geochemistry is co-located with sampling locations and sampling depths. This datasets also has the locations of small channels, and hollows that are on top of floodplain Meander C. These small channels funnel surface water from the hillslope through the floodplain and out to the river. All text datasets can be analyzed with software such as Excel or R. All shapefiles can be viewed with freely available R packages such as Leaflet.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Data for publication: "A fresh take: Seasonal changes in terrestrial freshwater inputs impact salt marsh hydrology and vegetation dynamics"

This data repository contains data associated with the manuscript "A fresh take: Seasonal changes in terrestrial freshwater inputs impact salt marsh hydrology and vegetation dynamics". This study was conducted at the Elkhorn Slough National Estuarine Research Reserve in Watsonville, California from October 2019 - June 2022. We sought to understand the role of shallow freshwater inputs from adjacent uplands on salt marsh hydrologic behavior and vegetation productivity. This dataset contains CSV files of the following: daily salt marsh subsurface water level and pore water conductivity, monthly vegetation survey measurements, soil core data. Estuary surface water level, conductivity, and local precipitation were downloaded from the National Estuarine Research Reserve System (Centralized Data Management Office) at https://cdmo.baruch.sc.edu/.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2026

Assessment of the hydromechanical higher-order MPM for the simulation of geotechnical problems

The Material Point Method (MPM) has been increasingly used to simulate large strain deformations. Linear interpolation functions are commonly used to perform the spatial integration. It is well-known that the discontinuities in the interpolation function derivatives induce shock-like artifacts known as ‘cell-crossing’ error. These errors compound with volumetric locking errors when used with hydromechanical formulations for porous media, where different velocity fields are used for each phase. The capabilities of higher-order MPM frameworks have not been explored for real-scale geotechnical problems. As such, this paper aims to assess, validate, and further discuss a higher-order B-spline MPM (BS-MPM) framework. First, the BS-MPM framework is verified against the large-strain oedometer consolidation problem. Second, the framework is validated against a real-scale slope failure experiment triggered by pore water pressure recharge. Landslide features that are captured using the higher-order framework are specifically highlighted, and results (e.g., pore water pressure and deformation) are validated with field measurements. A generally convergent numerical solution is observed when using cubic interpolation functions. Third, a footing penetration problem is simulated using the multi-patch BS-MPM. Trends are examined with respect to penetration velocity and variation in hydraulic conductivity. The BS-MPM framework ultimately presents a stabilized numerical solution that captures plausible hydromechanical interaction trends important in geotechnical engineering applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Investigation of the Effect of Injected CO 2 on the Morrow B Sandstone through Laboratory Batch Reaction Experiments: Implications for CO 2 Sequestration in the Farnsworth Unit, Northern Texas, USA

About one million tons of CO 2 have been injected into the Farnsworth unit to date. The target reservoir for CO 2 injection is the Morrow B Sandstone, which is primarily made of quartz with lesser amounts of albite, calcite, chlorite, and clay minerals. The impact of CO 2 injection on the mineralogy, porosity, and pore water composition of the Morrow B Sandstone is a major concern. Although numerical modeling studies suggest that porosity changes will be minimal, significant alterations to mineralogy and pore water composition are expected. Given the implications for CO 2 storage effectiveness and risk assessment, it is crucial to verify the accuracy of theoretical model predictions through laboratory experiments. To this end, batch reaction experiments were conducted to model conditions near an injection well in the Morrow B Sandstone and at locations further away, where the CO 2 has been diluted by formation water. The laboratory experiments involved submerging thin sections of both coarse- and fine-grained facies of the Morrow B Sandstone in formation water samples with varying levels of CO 2 . The experiments were conducted at the reservoir temperature of 75 °C. Two experimental runs were conducted, one lasting for 61 days and the other for 72 days. The initial fluid composition used in the second run was the same as in the first. The mineralogy changes in the thin sections were analyzed using SEM and the Tescan Integrated Mineral Analyzer (TIMA), while changes in the composition of the formation water were determined using ICP-AES. During each experiment, a thin layer of white fine-grained particles consisting mainly of dolomite and silica formed on the surface of the thin sections, leading to significant reductions in Ca, Mg, and Sr in the formation water. This outcome is consistent with numerical model predictions that dolomite would be the primary mineral that would react with injected CO 2 and that silica would be oversaturated in the formation water. Changes in mineral abundance in the thin sections themselves were much less systematic than in the theoretical modeling experiments, perhaps reflecting heterogeneities in the mineral grain size surface area to volume ratios and mineral distributions in the thin sections not considered in the numerical models.

58 GEOSCIENCES↗
DOE OSTI2022

Fast redox switches lead to rapid transformation of goethite in humid tropical soils: A Mössbauer spectroscopy study

Abstract Humid tropical forest soils experience frequent rainfall, which limits oxygen diffusion and creates redox heterogeneity in upland soils. In this study we gauged the effect of short‐term anoxic conditions on Fe mineralogy of relatively Fe‐ and C‐rich surface soils (C/Fe mole ratio ∼5) from a humid tropical forest in Puerto Rico. Soils subjected to 4‐d oxic/anoxic oscillation were characterized by selective chemical extractions, Mössbauer spectroscopy (MBS), and X‐ray diffraction. Chemical extraction data suggested that rapidly switching redox conditions had subtle effects on bulk Fe mineralogy. Mössbauer, on the other hand, indicated that (a) the soil Fe is a mixture of goethites of varying characteristics with minor contributions from ferrihydrite (<5%) and Fe(III)‐organic matter (OM) phases (∼10%), and (b) anoxic conditions rapidly transformed all forms of goethite to relatively stable Fe oxides. Such fast changes in goethite features could be due to rapid depletion and sorption of bio‐released structural Al or sorbed OM onto residual soil components. The rapid temporal changes in MBS parameters and corresponding pore water nominal oxidation state of C values suggest that Fe‐C transformations in these upland tropical soils are complex and intricately coupled. A comprehensive understanding of the fate of Fe, Al, and OM (Fe‐organic moieties) during redox switches and concurrent changes in pore water chemistry is critical for development of robust transport models in humid tropical soils, which are subject to episodic low‐redox events.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Sources and Variability of Nitrate on an Alaskan Hillslope Dominated by Alder Shrubs, Kougarok, Alaska, 2017 and 2018

Data provided include results of analyses of soil pore-water, soil moisture, and leaf litter samples collected at a Kougarok Hillslope site dominated by alder shrubs (KG_MM64) in the Seward Peninsula, Alaska during July and September 2017 and 2018. Samples were from surface soils in close proximity to 5 alder patches, collected upslope, within, and downslope of the alder patches. Pore water was analyzed for a comprehensive set of anions, cations, elemental analyses, and oxygen and nitrogen isotopes. Soil samples were collected for soil moisture determination. Leaf litter extracts were analyzed for carbon and nitrogen content and carbon and nitrogen isotopes. This dataset contains 3 *.csv files and 1 *.pdf file. The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a research effort to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy's Office of Biological and Environmental Research. The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska. Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy's Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Characterization of Contaminants and Mobility in WMA A-AX Boreholes D0006 and D0008

This study was initiated to determine if subsurface contaminants in the A-AX vadose zone at the Hanford site (boreholes D0006 and D0008) caused corrosion of nearby stainless steel well casings (299-E-24-19, 299-E25-46, and 299-E25-236) and, based on the type and distribution of contaminants, determine if contaminants are from one or more sources including a) the A-104 and/or A-105 tanks, b) the 242A evaporator, and c) the 200-E-286 ditch. A tiered approach was used for characterizing contaminants in vadose zone sediments starting with mobile and total contaminant concentrations (Tier 1), characterizing contaminant speciation (Tier 2), and measuring contaminant leaching (Tier 3). Total and mobile contaminant measurements at seven depths showed elevated sulfate and nitrate in all samples (130 to 280 ft depth), elevated chloride in five depths, and no elevated radionuclides except I-129 in D0006 at 206 to 208 ft depth. If these contaminants were initially acidic, stainless-steel corrosion would occur. However, because sediments likely have a high acid neutralization capacity, an acidic spill would have been neutralized within tens of feet, so casing corrosion would likely occur in shallow sediments. GEL labs data also shows low (but above natural) chromate from shallow to 170 ft depth, then higher chromate to 280 ft, suggesting a surface Cr spill or casing corrosion. GEL labs data also showed evidence of more than one plume, with deep nitrate, sulfate, and chloride migration, but only shallow tritium migration. Tritium should migrate nearly unretarded in the subsurface like nitrate and chloride. Elevated aqueous cations and anions in the D0006 206 to 208' depth pore water (SO 4 2- , NO 3 - , Na + , K + , Ca 2+ , Mg 2+ , Si) could be the result of acid disposal and calcite dissolution at shallow depth, with deeper migration of SO 4 2- , NO 3 - from acids and Ca 2+ and Mg 2+ from calcite. Elevated Si (160 mg/L) indicates dissolution of clays or other silicates, which can also occur in acids. Acid extractable metals did show elevated Cr (but not Fe, Ni, Mo, and Mn) above natural levels, which may indicate stainless-steel well corrosion or transport of metals from a shallow spill. The elevated I-129 in D0006 at 206 to 208' depth was low with 0.34 μg/g in pore water and 1.5 μg/g total extractable I-129 in the sediment, which indicates significant fraction of I-129 was bound in one or more precipitates. Although total I-129 was below detection limits in most extractions due to high molybdate interference, I-127 analysis provided some insight into potential precipitate phases. Total I-127 was mainly extracted by acetate or acetic acid (67%), which may be iodine in calcite. Inorganic carbon measurement identified 1.65% calcite, and total organic carbon (TOC) was below detection limits, so iodine was not associated with organic matter. Nearly all the I-127 was present as iodide. In 1-D leach experiments, I-127 as iodide leached from the sediment within 2 pore volumes. Due to high and dynamic molybdate leaching from the sediment and interference with I-129 analysis, there were few quantifiable I-129 measurements. The calculated molybdate release rates from the sediment suggested Mo was being released from the same precipitate phase, such as molybdate incorporated into calcite. Overall, because there was little radioactive contamination measured in D0006 and D0008 boreholes, potential releases from A-104 and A-105 did not reach this location south of the A tank farm. Elevated cations and anions found in D0006 and D0008 at depth as the result of acidic disposal could cause shallow stainless steel casing corrosion. The nearby 242A evaporator generally contained alkaline waste and tritium, but the nearby 200-E-286 ditch generally contained high Cl - liquid effluent, so these are unlikely to be acidic sources.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Use of Stable Mercury Isotopes to Assess Mercury and Methylmercury Transformation and Transport across Critical Interfaces from the Molecular to the Watershed Scale (Final Report)

This project titled “Use of Stable Mercury Isotopes to Assess Mercury and Methylmercury Transformation and Transport across Critical Interfaces from the Molecular to the Watershed Scale” represents a collaborative effort between the University of Michigan (Jason Demers, PI) and Oak Ridge National Laboratory (Scott Brooks, co-I). Much has been learned about mercury (Hg) cycling in stream ecosystems, and East Fork Poplar Creek (EFPC) in particular, through decades of previous research. Nevertheless, some of the most fundamental questions regarding the sources of bioavailable Hg and its transformation to toxic methylmercury (MeHg) have remained unanswered. These fundamental questions include: (1) what are the sources and biogeochemical processes that lead to the input of dissolved Hg to stream water across critical subsurface interfaces within stream ecosystems, and EFPC in particular? and (2) what are the sources and biogeochemical processes that control the production and fate of bioaccumulative MeHg within stream ecosystems, and in EFPC in particular? To address these fundamental questions, our project aimed to couple laboratory experiments and field observations, both utilizing natural abundance Hg stable isotope techniques, to identify the processes responsible for generating mobile, bioavailable dissolved Hg from recalcitrant legacy sources within critical subsurface zones (e.g., streambed hyporheic zone, riparian floodplain subsurface). We used the isotopic signature of this bioavailable dissolved Hg to track its mobilization across these critical interfaces in order to link diffuse subsurface sources of dissolved Hg with increases in surface water dissolved Hg flux measured at the watershed scale. Additionally, our research aimed to determine the isotopic composition of MeHg within these same critical subsurface zones. We directly assessed the isotopic composition of MeHg within biota in order to gain insight into which subsurface sources of inorganic Hg and toxic MeHg are available for bioaccumulation within the EFPC ecosystem. Net fluxes of dissolved Hg along the flow path of EFPC were shown to vary spatially and temporally. In the Upper EFPC, within the Y12 boundary, stream water flux of dissolved Hg consistently decreased between the outfall and the downstream boundary of Y12 (57% ± 29%, 1SD). Within the Upper EFPC, an assessment of Hg isotopic composition suggested that losses were strongly reaction-driven, although isotopic diagnostics did not conform to any known processes. Downstream of Y12, in the upper reach of the Lower EFPC, dissolved Hg fluxes tended to increase during the dormant season (net gain of 11-120%), and decrease during the growing season (net loss of 23% +/- 18%, 1SD). In the downstream-most reach of Lower EFPC, dissolved Hg fluxes increased by 12-108% in 9 out of 10 monthly assessments. Overall, diffuse fluxes from the non-Y12 watershed accounted for 34% (+/- 17%, 1SD) of all dissolved Hg exported during base flow. Within Lower EFPC, an assessment of Hg isotopic composition was consistent with the contribution of diffuse Hg inputs from high-concentration hotspots within riparian floodplains and streambed hyporheic pore water. To investigate remobilization of recalcitrant Hg from legacy sediment sources, we developed procedures that coupled isotopic analysis with sequential extractions of streambed sediment. We found that the proportion of weakly-bound Hg within EFPC streambed sediment was relatively small, but could still account for a large proportion of the annual flux of dissolved Hg from EFPC. These sequential extractions also showed that this weakly-bound Hg fraction could be replenished from the much larger fraction of recalcitrant Hg in sediment. The isotopic composition of these weakly-bound and remobilized recalcitrant Hg fractions within the sediment was consistent with high-concentration dissolved Hg hotspots within hyporheic pore water. Thus, this research provided novel evidence that legacy mercury sources within streambed sediment could provide an ongoing contribution of dissolved Hg to surface waters. Finally, we developed new methods for the direct determination of the MeHg isotopic composition of organisms, which allowed a more direct evaluation of inorganic Hg and MeHg sources accumulating in the food web. We found that fish and aquatic invertebrates in both EFPC and a regional background site obtained inorganic Hg and MeHg from multiple isotopically distinct sources, including sediment, suspended particulates, and periphyton. Photodemethylation was found to be an important reaction influencing MeHg dynamics at both sites. However, the balance of microbial methylation and demethylation processes differed between the two streams, with fractionation resulting from methylation and demethylation processes being relatively in balance within the regional background site, whereas microbial methylation appeared to be dominant over microbial demethylation within the EFPC ecosystem. Broadly, the application of Hg isotopic analysis in this study led to numerous novel insights regarding the biogeochemical cycling of Hg in stream ecosystems. This research project promoted the development of two new approaches, including the coupling of sequential extractions with Hg isotopic analysis to assess remobilization of recalcitrant Hg within sediments, and a new method for the isotopic analysis of MeHg isolated from environmental samples. Both of these efforts represent advances in capacity for the field of mercury isotopic analysis and environmental assessment. Overall, this study demonstrates that the application of Hg stable isotope techniques continues to provide new insights into the biogeochemical cycling of Hg in complex aquatic environments, both within the EFPC and beyond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Diatom influence on the production characteristics of hydrate-bearing sediments: Examples from Ulleung Basin, offshore South Korea

The Ulleung Basin Gas Hydrate field expeditions in 2007 (UBGH1) and 2010 (UBGH2) sought to assess the Basin's gas hydrate resource potential. Coring operations in both expeditions recovered evidence of gas hydrate, primarily as fracture-filling (or vein type) morphologies in mainly silt-sized, fine-grained sediment, but also as pore-occupying hydrate in the coarser-grained layers of interbedded sand and fine-grained systems. A commonality across many of these occurrences is the presence of diatoms in the fine-grained sediment. Here we tested fine-grained sediment (median grain size <12.5 μm) associated with hydrate occurrences at four UBGH2 sites (UBGH2-2-2, UBGH2-3, UBGH2-6 and UBGH2-11) to investigate potential impacts of diatoms on efforts to extract methane from hydrate, or to tap hydrocarbon reservoirs beneath hydrate-bearing sediment. Two key considerations are: the extent to which diatoms control sediment mechanical properties, and the extent to which pore-water freshening, which occurs as gas hydrate breaks down during resource extraction, alters the diatom control on sediment mechanical properties. We conducted experiments to measure sediment index properties, sedimentation behavior and compressibility to address these considerations. We relied on scanning electron microscope (SEM) imagery and X-ray powder diffraction (XRD) to characterize the sediment mineralogy. Our high-level findings are that at the ~20–45% (by volume) diatom concentrations observed at these UBGH2 sites, sediment compressibility increases with diatom content, but diatoms only appear to increase porosity and permeability at the highest diatom concentration (~45%). Our measurements suggest in situ compression indices of 0.35–0.55 and permeabilities on the order of 0.01milliDarcies (1 × 10 -17 m 2 ) can be anticipated at these sites. Importantly, these properties are not expected to vary significantly upon pore water freshening that accompanies gas hydrate dissociation during production.

58 GEOSCIENCES↗
DOE OSTI2022

Developing Water–Stable Pore–Partitioned Metal–Organic Frameworks with Multi–Level Symmetry for High–Performance Sorption Applications

Here a new perspective is proposed in the design of pore-space-partitioned MOFs that is focused on ligand symmetry properties sub-divided here into three hierarchical levels: 1) overall ligand, 2) ligand substructure such as backbone or core, and 3) the substituent groups. Different combinations of the above symmetry properties exist. Given the close correlation between nature of chemical moiety and its symmetry, such a unique perspective into ligand symmetry and sub-symmetry in MOF design translates into the influences on MOF properties. Five new MOFs have been prepared that exhibit excellent hydrothermal stability and high-performance adsorption properties with potential applications such as C 3 H 6 /C 2 H 4 and C 2 H 2 /CO 2 selective adsorption. The combination of high stability with high benzene/cyclohexane selectivity of ≈13.7 is also of particular interest.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Dimensionality effects on multicomponent ionic transport and surface complexation in porous media

Coulombic interactions between charged species in pore water and at surface/solution interfaces are of pivotal importance for multicomponent reactive transport in porous media. In this study, we investigate the impact of domain dimensionality on electrostatically coupled dispersion and surface-solution reactions during transport of acidic plumes and major ions in porous media. Column and quasi two-dimensional flow-through experiments were performed, with identical silica porous media and under the same advection-dominated conditions. Equal mass fluxes of different electrolyte solutions (i.e., HCl - pH ~ 2.8, NaBr - 100 mM, HCl - pH ~ 2.8 plus NaBr - 100 mM) were continuously injected in the 1-D and 2-D experiments and breakthrough curves of pH and major ions were measured at the outlet of the domains. The presence of pronounced ionic strength gradients in the transverse direction in the 2-D setup caused distinct retardation and transport behaviors of protons and major ions which were not observed in the one-dimensional column experiments. Furthermore, in the cases of salt electrolytes injection, considerably enhanced release of H + (>61%) from the quartz surface was observed in the multidimensional system compared to the one-dimensional setup. Reactive transport modeling was performed to reproduce the experimental outcomes and to analyse the coupling between transport processes, based on the Nernst-Planck formulation of diffusive/dispersive fluxes and on surface complexation reactions at the solid-solution interface. Electrostatic interactions between Na + , B – , and H + , and deprotonation of the quartz surface upon the formation of sodium outer-sphere complexes, are the primary controllers of the spatial and temporal features displayed by the pH and major ions measurements. The reactive transport simulations allowed us to interpret the experimental observations, to visualize the distribution and spatio-temporal evolution of dissolved and solid species, to identify a spatially heterogeneous zonation of Coulombic interactions with distinct behavior at the fringe and core of the injected plumes in the multidimensional setup, and to quantify the different components of the Nerst-Planck fluxes of the charged solutes. This study demonstrates that the domain dimensionality directly affects electrostatic interactions between charged aqueous species in the pore water and surface complexation reactions at the solid-solution interface. The non-trivial effects of dimensionality on multicomponent ionic transport result in a significantly different behavior in 1-D and 2-D systems.

58 GEOSCIENCES↗