Search NASA⌕ Search

SEARCH · Search NASA

Results for “dissolving”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2011

Successful Thrombolysis and Spasmolysis of Acute Leg Ischemia after Accidental Intra-arterial Injection of Dissolved Flunitrazepam Tablets

A 37-year-old man with known intravenous drug abuse presented in the surgical ambulatory care unit with acute leg ischemia after accidental intra-arterial injection of dissolved flunitrazepam tablets into the right femoral artery. A combination of anticoagulation, vasodilatation, and local selective and superselective thrombolysis with urokinase was performed to salvage the leg. As a result of the severe ischemia-induced pain, the patient had to be monitored over the complete therapy period on the intensive care unit with permanent administration of intravenous fluid and analgetics. We describe the presenting symptoms and the interventional technique, and we discuss the recent literature regarding the management of accidental intra-arterial injection of dissolved flunitrazepam tablets.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2019

Impact of dissolved salts on two-phase flow and boiling heat transfer in a natural circulation loop

Two-phase natural circulation and boiling experiments are conducted in this study with artificial seawater as a heat transfer fluid or process coolant. This experimental work is focused on understanding the role of dissolved salts in water on the steady state two-phase natural circulation flow rates. Mass flow rates were measured at different heat flux levels with artificial seawater, deionized water and tap water in the experimental loop. It was found that the average quasi-steady state mass flow rates were the same at any particular heat flux level regardless of the fluid being used. Artificial seawater coolant exhibited more stable natural circulation at higher heat flux as compared to the other two coolants. Mass flow measurements recorded at 2 s intervals show that magnitude of flow oscillations are much higher in case of tap water and deionized water. Also, high speed camera images revealed that the bubble departure diameters are smaller in seawater compared to tap or deionized water. This can be attributed to the increased local wettability due to the presence of dissolved salts in the fluid. Visual observations of the riser section showed that bubble coalescence and formation of slugs is inhibited in the seawater. These observations also explain the reduced pressure drop across test section when seawater was used as a coolant.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Impacts of elevated dissolved CO 2 on a shallow groundwater system: Reactive transport modeling of a controlled-release field test

We report one of the risks that CO 2 geological sequestration imposes on the environment is the impact of potential CO 2 /brine leakage on shallow groundwater. The reliability of reactive transport models predicting the response of groundwater to CO 2 leakage depends on a thorough understanding of the relevant chemical processes and key parameters affecting dissolved CO 2 transport and reaction. Such understanding can be provided by targeted field tests integrated with reactive transport modeling. A controlled-release field experiment was conducted in Mississippi to study the CO 2 -induced geochemical changes in a shallow sandy aquifer at about 50 m depth. The field test involved a dipole system in which the groundwater was pumped from one well, saturated with CO 2 at the pressure corresponding to the hydraulic pressure of the aquifer, and then re-injected into the same aquifer using a second well. Groundwater samples were collected for chemical analyses from four monitoring wells before, during and after the dissolved CO 2 was injected. In this paper, we present reactive transport models used to interpret the observed changes in metal concentrations in these groundwater samples. A reasonable agreement between simulated and measured concentrations indicates that the chemical response in the aquifer can be interpreted using a conceptual model that encompasses two main features: (a) a fast-reacting but limited pool of reactive minerals that responds quickly to changes in pH and causes a pulse-like concentration change, and (b) a slow-reacting but essentially unlimited mineral pool that yields rising metal concentrations upon decreased groundwater velocities after pumping and injection stopped. During the injection, calcite dissolution and Ca-driven cation exchange reactions contribute to a sharp pulse in concentrations of Ca, Ba, Mg, Mn, K, Li, Na and Sr, whereas desorption reactions control a similar increase in Fe concentrations. Finally, after the injection and pumping stops and the groundwater flow rate decreases, the dissolution of relatively slow reacting minerals such as plagioclase drives the rising concentrations of alkali and alkaline earth metals observed at later stages of the test, whereas the dissolution of amorphous iron sulfide causes slowly increasing Fe concentrations.

58 GEOSCIENCES↗
DOE OSTI2013

Silicate Carbonation in Supercritical CO2 Containing Dissolved H2O: An in situ High Pressure X-Ray Diffraction Study

Technological advances have been significant in recent years for managing environmentally harmful emissions (mostly CO2) resulting from combustion of fossil fuels. Deep underground geologic formations are emerging as reasonable options for long term storage of CO2 but mechanisms controlling rock and mineral stability in contact with injected supercritical fluids containing water are relatively unknown. In this paper, we discuss mineral transformation reactions occurring between supercritical CO2 containing water and the silicate minerals forsterite (Mg2SiO4), wollastonite (CaSiO3), and enstatite (MgSiO3). This study utilizes newly developed in situ high pressure x-ray diffraction (HXRD) and in situ infra red (IR) to examine mineral transformation reactions. Forsterite and enstatite were selected as they are important minerals present in igneous and mafic rocks and have been the subject of a large number of aqueous dissolution studies that can be compared with non-aqueous fluid tests in this study. Wollastonite, classified as a pyroxenoid (similar to a pyroxene), was chosen as a suitably fast reacting proxy for examining silicate carbonation processes associated with a wet scCO2 fluid as related to geologic carbon sequestration. The experiments were conducted under modest pressures (90 to 160 bar), temperatures between 35° to 70° C, and varying concentrations of dissolved water. Under these conditions scCO2 contains up to 3,500 ppm dissolved water.

carbon sequestration↗
DOE OSTI2021

Decoupling of particles and dissolved iron downstream of Greenlandic glacier outflows

Glaciers can be a significant and locally dominant source of iron (Fe), a biologically essential micronutrient, in high latitude coastal seas. The vast majority of this glacial Fe delivery is associated with particles, yet the speciation of the solid-phase Fe and specifically the relationships that govern exchange between particulate and dissolved Fe phases in these environments are poorly described. Here, in this work, we performed measurements of in situ dissolved Fe (dFe) along meltwater and particle plumes in three transects around Disko Bay and Ameralik Fjord (West Greenland). Measurements of dFe were combined with Fe K-edge X-ray absorption spectroscopy analysis of ~40 suspended sediment samples obtained from the same transects and from select depth profiles down to 300 m. We observed relatively constant dFe levels (4 to 10 nM for nearly all dFe measurements) across fjords with widely varying particulate Fe(II) contents (from 20 to 90% Fe(II)), indicating that dFe concentrations had little dependence on the oxidation state of Fe in the suspended sediment. Particulate Fe data were grouped by underlying bedrock geology, with suspended sediment consisting of 80-90% biotite-like Fe(II) in fjords with Precambrian shield geology and poorly-ordered Fe(III) particles (<20-30% Fe(II)) in one fjord with suspended sediments derived from tertiary basalts. Our characterization data indicated no significant change in the average Fe oxidation state and bonding environment of particles along the fjord transects, implying that Fe(II) in biotite-like coordination is not a readily labile Fe form on this spatial scale. Finally, our results suggest that dFe in these glacially-modified coastal waters is buffered at a relatively constant low nM concentration due to factors other than particle Fe mineralogy and that glacier-derived Fe phases are relatively inert on this spatial scale.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

Analysis of permeability change in dissolving rough fractures using depth-averaged flow and reactive transport models

Many geophysical problems and engineering applications involve fluid flow through evolving faults and fractures. These situations are typical in CO 2 injection scenarios where supercritical CO 2 or CO 2 –saturated fluids are able to dissolve the solid matrix. Dissolution or precipitation within a fracture could lead to self-reinforcing or self-limiting behavior due to feedbacks from changes in permeability (k). There is limited predictive understanding of this phenomenon. Here, we investigated the case of fracture dissolution using a two-dimensional depth-averaged reactive transport model. The model simulated an acidic fluid dissolving a three-dimensional rough fracture. We observed different dissolution patterns across a wide range of geometric properties and different Peclet and Damkohler numbers (960 cases total). Despite this variation, a persistent linear increase in k with time (t) roughly manifested once the dissolution front advanced through the fracture. The time rate of change of k (k/t) is roughly constant for all simulations. The modeled rate is consistent with a theoretical value based on the parallel plates model and with experimentally derived values. Finally, the results confirm the common presence of linear time-dependence of fracture k due to self-reinforcement.

58 GEOSCIENCES↗
DOE OSTI2022

Molecular structures of dissolved and colloidal As V –Fe III complexes and their roles in the mobilization of As V under strongly acidic conditions

The effect of high concentration of iron (Fe III ) on the speciation and mobility of arsenic (As) under strongly acidic conditions remains unclear. This work studied the redistribution and speciation of As V and Fe III at Fe/As molar ratio of 1–14 and pH 1.5–2.0 in the dissolved, colloidal, and solid phases. Results showed that the elevated Fe III induced the decomposition of the precipitated poorly crystalline ferric arsenate by forming dissolved (< 3 kDa) and colloidal (3 kDa–0.1 µm) As–Fe complexes. The fraction of particulate As (> 0.1 µm) decreased from 70–90% to less than 20% when the Fe/As molar ratio increased from 1 to 14. The particle size of the bulk samples decreased significantly with the increase of Fe III concentration. The FTIR results suggested that AsV in dissolved/colloidal As–Fe complexes dominantly occurred as HAsO 4 2– species. The EXAFS results indicated that each HAsO 4 2– coordinated with approximately two Fe atoms in dissolved/colloidal As–Fe complexes at Fe/As ≥ 2. Furthermore, the findings suggest that high aqueous Fe III concentration can promote the mobility of As by forming dissolved/colloidal Fe–As complexes in acidic waters, potentially accelerating As transport from source to downstream in acid mine drainage systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Removal of dissolved humic acid from water by photocatalytic oxidation using a silver orthophosphate semiconductor

Graphical abstract: Display Omitted Highlights: ► The photocatalytic property of a silver orthophosphate (Ag{sub 3}PO{sub 4}) was investigated for humic acid degradation. ► The Ag{sub 3}PO{sub 4} shows high photocatalytic activity under visible light. ► The photocatalytic activity was greatly improved by employing the precipitation method. -- Abstract: In order to remove dissolved organic matter such as humic acid from water, a silver orthophosphate (Ag{sub 3}PO{sub 4}) was newly employed as a heterogeneous photocatalyst. Here, Ag{sub 3}PO{sub 4} was prepared by simple ion-exchange and precipitation methods, and the physico-chemical properties were characterized by X-ray diffraction, ultraviolet–visible diffuse reflectance spectroscopy, scanning electron microscopy, particle distribution measurements and Brunauer–Emmett–Teller (BET) analysis. The degradation of humic acid was faster over Ag{sub 3}PO{sub 4} catalyst than over conventional TiO{sub 2} (P-25). The total photocatalytic properties were improved by employing not an ion-exchange method but a precipitation method; humic acid degradation was performed with a removal ratio of dissolved organic carbon of 75% under visible light (λ = 451 nm) for 2-h irradiation.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Assessing chromophoric dissolved organic matter (CDOM) distribution, stocks, and fluxes in Apalachicola Bay using combined field, VIIRS ocean color, and model observations

Understanding the role of estuarine-carbon fluxes is essential to improve estimates of the global carbon budget. Dissolved organic matter (DOM) plays an important role in aquatic carbon cycling. Here, the chromophoric fraction of DOM (CDOM) can be readily detected via in situ and remotely-sensed optical measurements. DOM properties, including CDOM absorption coefficient at 412 nm (a g 412) and dissolved organic carbon (DOC) concentrations were examined in Apalachicola Bay, a national estuarine research reserve located in the northeast Gulf of Mexico, using in situ and satellite observations during the spring and fall of 2015. Synoptic and accurate representation of estuarine-scale processes using satellite ocean color imagery necessitates the removal of atmospheric contribu- tion (~90%) to signals received by satellite sensors to successfully link to in situ observations. Three atmospheric correction schemes (e.g., Standard NIR correction, Iterative NIR correction, and SWIR correction) were tested first to find a suitable correction scheme for the VIIRS imagery in low to moderately turbid Apalachicola Bay. The iterative NIR correction performed well, and validation showed high correlation (R 2 = 0.95, N = 25) against in situ light measurements. A VIIRS-based CDOM algorithm was developed (R 2 = 0.87, N = 9) and validated (R 2 = 0.76, N = 20, RMSE = 0.29 m -1 ) against in situ observations. Subsequently, ag412 was used as a proxy of DOC in March (DOC = 1.08 + 0.94 × a g 412,R 2 =0.88, N = 13)and in November (DOC= 1.61 + 1.33 × a g 412, R 2 = 0.83, N = 24) to derive DOC maps that provided synoptic views of DOC distribution, sources, and their transport to the coastal waters during the wet and dry seasons. The estimated DOC stocks were ~3.71 × 10 6 kg C in March and ~4.07 × 10 6 kg C in November over an area of ~560 km2. Volume flux (out of the bay) almost doubled for March 24 (735 m 3 s -1 ) relative to November 4 (378 m 3 s -1 ). However, estimates of DOC fluxes exported out of the bay from model-derived currents and satellite-derived DOC were only marginally greater in March (0.163 × 10 6 kg C d -1 ) than in November (0.124 × 10 6 kg C d -1 ) and reflected greater DOC stocks in the fall. Finally, the combination of satellite-, field-, and model-based observations revealed the strong linkage between the Apalachicola River plume, a major source of DOM, and the overall hydrodynamic forcing that controlled distributions of CDOM abundance, DOC concentration, stocks, and fluxes in the bay.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

Dissolved organic matter reduces the effectiveness of sorbents for mercury removal

Mercury (Hg) contamination of soils and sediments impacts numerous environments worldwide and constitutes a challenging remediation problem. In this study, we evaluate the impact of dissolved organic matter (DOM) on the effectiveness of eight sorbent materials considered for Hg remediation in soils and sediments. The materials include both engineered and unmodified materials based on carbon, clays, mesoporous silica and a copper alloy. Initially, we investigated the kinetics of Hg(II) complexation with DOM for a series of Hg:DOM ratios. Steady-state Hg-DOM complexation occurred within 48 to 120 h, taking longer time at higher Hg:DOC (dissolved organic carbon) molar ratios. In subsequent equilibrium experiments, Hg(II) was equilibrated with DOM at a defined Hg:DOC molar ratio (2.4 · 10 –6 ) for 170 h and used in batch experiments to determine the effect of DOM on Hg partition coefficients and sorption isotherms by comparing Hg(II) and Hg-DOM. Hg sorption capacities of all sorbents were severely limited in the presence of DOM as a competing ligand. Thiol-SAMMS®, SediMite™ and pine biochar were most effective in reducing Hg concentrations. While pine biochar and lignin-derived carbon processed at high temperatures released negligible amounts of anions into solution, leaching of sulfate and chloride was observed for most engineered sorbent materials. Sulfate may stimulate microbial communities harboring sulfate reducing bacteria, which are considered one of the primary drivers of microbial mercury methylation in the environment. Here, the results highlight potential challenges arising from the application of sorbents for Hg remediation in the field.

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

Disinfection byproducts formed during drinking water treatment reveal an export control point for dissolved organic matter in a subalpine headwater stream

Changes in climate, season, and vegetation can alter organic export from watersheds. While an accepted tradeoff to protect public health, disinfection processes during drinking water treatment can adversely react with organic compounds to form disinfection byproducts (DBPs). By extension, DBP monitoring can yield insights into hydrobiogeochemical dynamics within watersheds and their implications for water resource management. In this study, we analyzed temporal trends from a water treatment facility that sources water from Coal Creek in Crested Butte, Colorado. These trends revealed a long-term increase in haloacetic acid and trihalomethane formation over the period of 2005-2020. Additionally, disproportionate export of dissolved organic carbon and formation of DBPs that exceeded regulatory guidelines were consistently recorded in association with late spring freshet. Synoptic sampling of the creek in 2020 and 2021 identified a biogeochemical hotspot for organic carbon export in the upper domain of the watershed that contained a prominent fulvic acid-like fluorescent signature. DBP formation potential analyses from this domain yielded similar ratios of dominant DBP species to those formed at the drinking water facility. Spectrometric qualitative analyses of pre and post-reacted waters with hypochlorite indicated ligninlike and condensed hydrocarbon-like molecules were the major reactive chemical classes during chlorine-based disinfection. This study demonstrates how drinking water quality archives can be coupled with synoptic sampling to identify and understand export control points for dissolved organic matter. Resultant understanding can be applied in water treatment and watershed management plans to improve drinking water quality sourced from analogous watersheds.

47 OTHER INSTRUMENTATION↗
DOE OSTI2023

Voltammetric Measurement of Rates and Energetics for Surface Methoxylation of Si(100) in Methanol with Dissolved Electron Acceptors Using Si Ultramicroelectrodes

The steady-state voltammetric responses of n-type Si(100) semiconductor ultramicroelectrodes (SUMEs) immersed in air- and water-free methanolic electrolytes have been measured. The response characteristics of these SUMEs in the absence of illumination were modeled and understood through a framework that describes the distribution of the applied potential across the semiconductor/electrolyte contact using four discrete regions: the semiconductor space charge, surface, Helmholtz, and diffuse layers. The latter region was described by the full Gouy–Chapman model. This framework afforded insight on how relevant parameters such as the semiconductor band edge potentials, the reorganization energies for charge transfer, the standard potential of redox species in solution, the density and energy of surface state populations, and the presence of an insulating (tunneling) layer individually and collectively dictate the observable current–potential responses. With this information, the methoxylation of Si surfaces was evaluated by analysis of the change in voltammetric responses during the course of prolonged immersion in methanol. Here, the electrochemical data were consistent with a surface methoxylation mechanism that depended on the standard potential of redox species dissolved in solution. Estimates of the enthalpies of adsorption as well as the potential-dependent rate constant for surface methoxylation were obtained. Collectively, these measurements supported the contention that the rates of Si surface reactions can be systematically tuned by exposure to dissolved outer-sphere electron acceptors. Moreover, the data represent the quantitative utility of voltammetry with SUMEs for the measurement of semiconductor/liquid contacts.

14 SOLAR ENERGY↗
DOE OSTI2022

Real-Time Monitoring of Gas-Phase and Dissolved CO 2 Using a Mixed-Matrix Composite Integrated Fiber Optic Sensor for Carbon Storage Application

Novel chemical sensors that improve detection and quantification of CO 2 are critical to ensuring safe and cost-effective monitoring of carbon storage sites. Fiber optic (FO) based chemical sensor systems are promising field-deployable systems for real-time monitoring of CO 2 in geological formations for long-range distributed sensing. Here, a mixed-matrix composite integrated FO sensor system was developed with a purely optical readout that reliably operates as a detector for gas-phase and dissolved CO 2 . A mixed-matrix composite sensor coating consisting of plasmonic nanocrystals and hydrophobic zeolite embedded in a polymer matrix was integrated on the FO sensor. The mixed-matrix composite FO sensor showed excellent reversibility/stability in a high humidity environment and sensitivity to gas-phase CO 2 over a large concentration range. This remarkable sensing performance was enabled by using plasmonic nanocrystals to significantly enhance the sensitivity and a hydrophobic zeolite to effectively mitigate interference from water vapor. The sensor exhibited the ability to sense CO 2 in the presence of other geologically relevant gases, which is of importance for applications in geological formations. A prototype FO sensor configuration which possesses a robust sensing capability for monitoring dissolved CO 2 in natural water was demonstrated. Reproducibility was confirmed over many cycles, both in a laboratory setting and in the field. More importantly, we demonstrated on-line monitoring capabilities with a wireless telemetry system, which transferred the data from the field to a website. The combination of outstanding CO 2 sensing properties and facile coating processability makes this mixed-matrix composite FO sensor a good candidate suitable for practical carbon storage applications.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

Ammonium Additives to Dissolve Lithium Sulfide through Hydrogen Binding for High-Energy Lithium–Sulfur Batteries

In rechargeable Li-S batteries, the uncontrollable passivation of electrodes by highly insulating Li2S limits sulfur utilization, increases polarization and decreases cycling stability. Dissolving Li2S in organic electrolyte is a facile solution to maintain the active reaction interface between electrolyte and sulfur cathode, and thus address the above issues. Herein, ammonium salts are demonstrated as effective additives to promote the dissolution of Li2S to 1.25 M in DMSO solvent at room temperature. NMR measurements show that the strong hydrogen binding effect of N-H groups plays a critical role in dissolving Li2S by forming complex ligands with S2- anions coupled with the solvent’s solvating surrounding. Ammonium additives in electrolyte can also significantly improve the oxidation kinetics of Li2S, therefore enables the direct use of Li2S as cathode material in Li-S battery system in the future. This provides a new approach to manage the solubility of lithium sulfides through cation coordination with sulfide anion.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2025

Dissolved CO 2 Modulates the Electrochemical Capacitance on Gold Electrodes

The presence of CO 2 at an electrified interface between an aqueous electrolyte and a metal electrode is the prerequisite for many electrochemical CO 2 capture technologies. To understand the behavior of dissolved CO 2 at an aqueous electrified interface, we characterized the electrochemical interface of planar gold electrodes with cyclic voltammetry, electrochemical impedance spectroscopy (EIS), electrochemical surface plasmon resonance (EC–SPR), and attenuated total reflectance surface-enhanced infrared spectroscopy (ATR–SEIRAS). Under all investigated conditions, we observed a decrease in the electrochemical capacitance upon saturation of the electrolyte with CO 2 , as compared to an electrolyte saturated with Ar. EIS and EC–SPR showed that this capacitance reduction was also potential dependent: it reached a minimum near the point of zero charge and became more significant as the applied potential moved further away from the point of zero charge. Hybrid quantum–classical simulations of the gold/aqueous electrolyte interface indicate that bicarbonate decreases the capacitance and modifies the composition of the electric double layer. In addition to the binding of bicarbonate under positive bias, we propose that molecular CO 2 can be induced by applied potential to concentrate in the diffuse layer of the electric double layer, leading to a reduction in the electrochemical capacitance under both negative and positive bias. Furthermore, this work advances the understanding of non-Faradaic effects of dissolved CO 2 at aqueous electrified interfaces of relevance for electrochemical CO 2 capture.

25 ENERGY STORAGE↗
DOE OSTI2025

Dissolved Oxygen Redox as the Source of Hydrogen Peroxide and Hydroxyl Radical in Sonicated Emulsive Water Microdroplets

Sonicated emulsive water microdroplets (SEWMs) accelerate and enable a variety of catalyst-free chemical transformations. However, significant unanswered questions remain regarding the chemical intermediates they form and their possible redox origin. In this study, we identified dissolved O 2 as the primary originator of reactive oxygen species (ROS) such as OH• and H 2 O 2. We uncovered the role of dissolved O 2 redox by using a combination of microelectrochemical methods to detect H 2 O 2 , isotopic methods to identify the source of H 2 O 2 , and a combination of electron spin resonance and the DMPO spin trap to detect radicals such as OH•. Notably, we found that H 2 O 2 production is correlated with O 2 content via a reduction pathway enabled by a sufficiently large reducing power that can additionally generate H 2 and even perform Pb electroless deposition on Au and Cu metal substrates. Building on our findings, continuous O 2 bubbling of SEWMs showed accumulation of H 2 O 2 up to ∼88 mM in the aqueous phase within 1 h of sonication, demonstrating the scale-up promise of this method. Distinct to sonochemistry of a single phase, this study advances our understanding of the confluence of redox and chemical reaction mechanisms within SEWMs as a biphasic system. This insight paves the way for improving their reaction kinetics, yield, and selectivity, positioning these attractive redox microreactors as alternatives to traditional electrolyzers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Dissolved Nutrient Retention Dynamics in River Networks: A Modeling Investigation of Transient Flow and Scale Effects

In this paper, we use a dynamic network flow model, coupled with a transient storage zone biogeochemical model, to simulate dissolved nutrient removal processes at the channel network scale. We have explored several scenarios in respect of the combination of rainfall variability, and the biological and geomorphic characteristics of the catchment, to understand the dominant controls on removal and delivery of dissolved nutrients (e.g., nitrate). These model-based theoretical analyses suggested that while nutrient removal efficiency is lower during flood events compared to during baseflow periods, flood events contribute significantly to bulk nutrient removal, whereas bulk removal during baseflow periods is less. This is due to the fact that nutrient supply is larger during flood events; this trend is even stronger in large rivers. However, the efficiency of removal during both periods decreases in larger rivers, however, due to (i) increasing flow velocities and thus decreasing residence time, and (ii) increasing flow depth, and thus decreasing nutrient uptake rates. Besides nutrient removal processes can be divided into two parts: in the main channel and in the hyporheic transient storage zone. When assessing their relative contributions the size of the transient storage zone is a dominant control, followed by uptake rates in the main channel and in the transient storage zone. Increasing size of the transient storage zone with downstream distance affects the relative contributions to nutrient removal of the water column and the transient storage zone, which also impacts the way nutrient removal rates scale with increasing size of rivers. Intra-annual hydrologic variability has a significant impact on removal rates at all scales: the more variable the streamflow is, compared to mean discharge, the less nutrient is removed in the channel network. A scale-independent first order uptake coefficient, ke, estimated from model simulations, is highly dependent on the relative size of the transient storage zone and how it changes in the downstream direction, as well as the nature of hydrologic variability.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Concentration‐Discharge Relationships of Dissolved Rhenium in Alpine Catchments Reveal Its Use as a Tracer of Oxidative Weathering

Abstract Oxidative weathering of sedimentary rocks plays an important role in the global carbon cycle. Rhenium (Re) has been proposed as a tracer of rock organic carbon (OC petro ) oxidation. However, the sources of Re and its mobilization by hydrological processes remain poorly constrained. Here, we examine dissolved Re as a function of water discharge, using samples collected from three alpine catchments that drain sedimentary rocks in Switzerland (Erlenbach and Vogelbach) and Colorado, USA (East River). The Swiss catchments reveal a higher dissolved Re flux in the catchment with higher erosion rates, but have similar [Re]/[Na + ] and [Re]/[SO 4 2− ] ratios, which indicate a dominance of Re from OC petro . Despite differences in rock type and hydro‐climatic setting, the three catchments have a positive correlation between river water [Re]/[Na + ] and [Re]/[SO 4 2− ] and water discharge. We propose that this reflects preferential routing of Re from a near‐surface, oxidative weathering zone. The observations support the use of Re as a proxy to trace rock‐organic carbon oxidation, and suggest it may be a hydrological tracer of vadose zone processes. We apply the Re proxy and estimate CO 2 release by OC petro oxidation of 5.7 +6.6 / −2.0 tC km −2 yr −1 for the Erlenbach. The overall weathering intensity was ∼40%, meaning that the corresponding export of unweathered OC petro in river sediments is large, and the findings call for more measurements of OC petro oxidation in mountains and rivers as they cross floodplains.

54 ENVIRONMENTAL SCIENCES↗