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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 271 records · Page 15

Estimating Internal Stress of an Alteration Layer Formed on Corroded Boroaluminosilicate Glass through Spectroscopic Ellipsometry Analysis

Aqueous corrosion of glass may result in the formation of an alteration layer in the glass surface of which chemical composition and network structure are different from those of the bulk glass. Since corrosion occurs far below the glass-transition temperature, the alteration layer cannot fully relax to the new structure with the lowest possible energy. Molecular dynamics simulations suggested that such a network will contain highly strained chemical bonds, which can be manifested as a stress in the alteration layer. Common techniques to measure stress in thin films or surface layers were found inadequate for thick monolithic glass samples corroded in water. Here, we explored the use of spectroscopic ellipsometry to test the presence of internal stress in the alteration layer formed by aqueous corrosion of glass. Furthermore, a procedure for analyses of spectroscopic ellipsometry data to determine birefringence in the alteration layer was developed. Findings with the established fitting procedure suggested that a stress builds up in the corroded surface layer of a boroaluminosilicate glass if there is a change in relative humidity, pH, or electrolyte concentration of the environment to which the glass surface is exposed. A similar process may occur in other types of glass, and it may affect the surface properties of corroded glass objects.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Carbon Dioxide Production in Bedrock Beneath Soils Substantially Contributes to Forest Carbon Cycling

Abstract Soils are widely considered the primary terrestrial organic matter pool mediating carbon transactions with the atmosphere and groundwater. Because soils are both a host and a product of rhizosphere activity, they are thought to mark the location where photosynthetic fixation of carbon dioxide (CO 2 ) is balanced by the oxidation of organic matter. However, in many terrestrial environments, the rhizosphere extends below soils and into fractured bedrock, and it is unknown if the resulting biological and hydrologic dynamics in bedrock have a significant impact on carbon cycling. Here we show substantial production of CO 2 in weathered bedrock at 4–8 m below the thin soils (<0.5 m thick) of a Northern California forest using innovative monitoring technology for sampling gases and water in fractured rock. The deep CO 2 production supports a persistent upward flux of CO 2(g) year‐round from bedrock to soil, constituting between 2% and 29% of the average daily CO 2 efflux from the land surface. When water is rapidly transported across the fractured bedrock vadose zone, nearly 50% of the CO 2 produced in the bedrock dissolves into water, promoting water‐rock interaction and export of dissolved inorganic carbon (DIC) from the unsaturated zone to groundwater, constituting as much as 80% of the DIC exiting the hillslope. Such CO 2 production in weathered bedrock is subject to unique moisture, temperature, biological, and mineralogical conditions which are currently missing from terrestrial carbon models.

54 ENVIRONMENTAL SCIENCES↗

Arctic Permafrost Thawing Enhances Sulfide Oxidation

Permafrost degradation is altering biogeochemical processes throughout the Arctic. Thaw-induced changes in organic matter transformations and mineral weathering reactions are impacting fluxes of inorganic carbon (IC) and alkalinity (ALK) in Arctic rivers. However, the net impact of these changing fluxes on the concentration of carbon dioxide in the atmosphere (pCO 2 ) is relatively unconstrained. Resolving this uncertainty is important as thaw-driven changes in the fluxes of IC and ALK could produce feedbacks in the global carbon cycle. Enhanced production of sulfuric acid through sulfide oxidation is particularly poorly quantified despite its potential to remove ALK from the ocean-atmosphere system and increase pCO 2 , producing a positive feedback leading to more warming and permafrost degradation. In this work, we quantified weathering in the Koyukuk River, a major tributary of the Yukon River draining discontinuous permafrost in central Alaska, based on water and sediment samples collected near the village of Huslia in summer 2018. Using measurements of major ion abundances and sulfate (SO 4 2- ) sulfur ( 34 S/ 32 S) and oxygen ( 18 O/ 16 O) isotope ratios, we employed the MEANDIR inversion model to quantify the relative importance of a suite of weathering processes and their net impact on pCO 2 . Calculations found that approximately 80% of SO 4 2- in mainstem samples derived from sulfide oxidation with the remainder from evaporite dissolution. Moreover, 34 S/ 32 S ratios, 13 C/ 12 C ratios of dissolved IC, and sulfur X-ray absorption spectra of mainstem, secondary channel, and floodplain pore fluid and sediment samples revealed modest degrees of microbial sulfate reduction within the floodplain. Weathering fluxes of ALK and IC result in lower values of pCO 2 over timescales shorter than carbonate compensation (~10 4 yr) and, for mainstem samples, higher values of pCO 2 over timescales longer than carbonate compensation but shorter than the residence time of marine (~10 7 yr). Furthermore, the absolute concentrations of and Mg 2+ in the Koyukuk River, as well as the ratios of SO 4 2- and Mg 2+ to other dissolved weathering products, have increased over the past 50 years. Through analogy to similar trends in the Yukon River, we interpret these changes as reflecting enhanced sulfide oxidation due to ongoing exposure of previously frozen sediment and changes in the contributions of shallow and deep flow paths to the active channel. Overall, these findings confirm that sulfide oxidation is a substantial outcome of permafrost degradation and that the sulfur cycle responds to permafrost thaw with a timescale-dependent feedback on warming.

54 ENVIRONMENTAL SCIENCES↗

Deep anoxic aquifers could act as sinks for uranium through microbial-assisted mineral trapping

Uptake of uranium (U) by secondary minerals, such as carbonates and iron (Fe)-sulfides, that occur ubiquitously on Earth, may be substantial in deep anoxic environments compared to surficial settings due to different environment-specific conditions. Yet, knowledge of U reductive removal pathways and related fractionation between 238 U and 235 U isotopes in deep anoxic groundwater systems remain elusive. Here we show bacteria-driven degradation of organic constituents that influences formation of sulfidic species facilitating reduction of geochemically mobile U(VI) with subsequent trapping of U(IV) by calcite and Fe-sulfides. The isotopic signatures recorded for U and Ca in fracture water and calcite samples provide additional insights on U(VI) reduction behaviour and calcite growth rate. The removal efficiency of U from groundwater reaching 75% in borehole sections in fractured granite, and selective U accumulation in secondary minerals in exceedingly U-deficient groundwater shows the potential of these widespread mineralogical sinks for U in deep anoxic environments.

36 MATERIALS SCIENCE↗

Tectonic and geological setting influence hot spring microbiology

Hydrothermal systems form at divergent and convergent boundaries of lithospheric plates and within plates due to weakened crust and mantle plumes, playing host to diverse microbial ecosystems. Little is known of how differences in tectonic setting influence the geochemical and microbial compositions of these hydrothermal ecosystems. Here, for this work, coordinated geochemical and microbial community analyses were conducted on 87 high-temperature (>65°C) water and sediment samples from hot springs in Yellowstone National Park, Wyoming, USA ( n = 41; mantle plume setting), Iceland ( n = 41, divergent boundary), and Japan ( n = 5; convergent boundary). Region-specific variation in geochemistry and sediment-associated 16S rRNA gene amplicon sequence variant (ASV) composition was observed, with 16S rRNA gene assemblages being nearly completely distinguished by region and pH being the most explanatory parameter within regions. Several low abundance ASVs exhibited cosmopolitan distributions across regions, while most high-abundance ASVs were only identified in specific regions. The presence of some cosmopolitan ASVs across regions argues against dispersal limitation primarily shaping the distribution of taxa among regions. Rather, the results point to local tectonic and geologic characteristics shaping the geochemistry of continental hydrothermal systems that then select for distinct microbial assemblages. These results provide new insights into the co-evolution of hydrothermal systems and their microbial communities.

59 BASIC BIOLOGICAL SCIENCES↗

Metabolic multireactor: Practical considerations for using simple oxygen sensing optodes for high-throughput batch reactor metabolism experiments

We present a system for carrying out small batch reactor oxygen consumption experiments on water and sediment samples for environmental questions. In general, it provides several advantages that can help researchers achieve impactful experiments at relatively low costs and high data quality. In particular, it allows for multiple reactors to be operated and their oxygen concentrations to be measured simultaneously, providing high throughput and high time-resolution data, which can be advantageous. Most existing literature on similar small batch-reactor metabolic studies is limited to either only a few samples, or only a few time points per sample, which can restrict the ability for researchers to learn from their experiments. The oxygen sensing system is based very directly on the work of Larsen, et al. [2011], and similar oxygen sensing technology is widely used in the literature. As such we do not delve deeply into the specifics of the fluorescent dye sensing mechanism. Instead, we focus on practical considerations. We describe the construction and operation of the calibration and experimental systems, and answer many of the questions likely to come up when other researchers choose to build and operate a similar system themselves (questions we ourselves had when we first built the system). In this way, we hope to provide an approachable and easy to use research article that can help other researchers construct and operate a similar system that can be tailored to ask their own research questions, with a minimum of confusion and missteps along the way.

3D printing↗

CO2 response (ACi) gas exchange, calculated Vcmax & Jmax parameters, Feb2016-May2016, PA-SLZ, PA-PNM: Panama

This data package contains CO2 response (ACi) gas exchange and fitted Vcmax and Jmax parameters measured on sunlit canopy trees within the NGEE Tropics sites Parque Natural Metropolitano (PA-PNM) and Bosque Protector San Lorenzo (PA-SLZ) in Panama. Measurements were taken on a monthly basis from February to May of 2016. This data was collected as part of the 2016 El Niño-Southern Oscillation (ENSO) campaign. Included in this data package are two Excel files with data (2016ENSO_Panama_ACi, 2016ENSO_Panama_Fitted_Vcmax_Jmax) and three Excel files with associated metadata. Also included is a Word document (Metadata_description_2016_ENSO_Panama) with details such as data collection methods, equipment used, and site information and a pdf (NGEE_Tropics_ENSO_Aci_Protocol_V2). See related datasets for further sample details, leaf water potential, LMA, leaf spectra, diurnal gas exchange and leaf chemistry. VERSION 2 update. The identification of a species from the PNM site has been corrected as follows: the identification of the tree initially identified as Pseudosamanea guachapele (ALBIED) has been revised to Albizia adinocephala (ALBIAD). The updated data package includes revised data, metadata and protocol documents updated to reflect this change.

54 ENVIRONMENTAL SCIENCES↗

Diurnal leaf gas exchange survey, Feb2016-May2016, PA-SLZ, PA-PNM: Panama

This data package contains the results of a diurnal leaf gas exchange survey measured on sunlit canopy trees within the NGEE Tropics sites Parque Natural Metropolitano (PA-PNM) and Bosque Protector San Lorenzo (PA-SLZ) in Panama. Measurements were taken on a monthly basis from February to May of 2016. This data was collected as part of the 2016 El Niño-Southern Oscillation (ENSO) campaign. Included in this data package are two Excel files with data (2016ENSO_Panama_DiurnalGasEx, 2016ENSO_Panama_AreaCorrections) and additional Excel files with associated metadata. Also included is a Word document (Metadata_description_2016_ENSO_Panama) with details such as data collection methods, equipment used, and site information. See related datasets for further sample details, leaf water potential, LMA, leaf spectra, other gas exchange and leaf chemistry. VERSION 2 update. The identification of a species from the PNM site has been corrected as follows: the identification of the tree initially identified as Pseudosamanea guachapele (ALBIED) has been revised to Albizia adinocephala (ALBIAD). The updated data package includes revised data, metadata and protocol documents updated to reflect this change.

54 ENVIRONMENTAL SCIENCES↗

Leaf mass area, Feb2016-May2016, PA-SLZ, PA-PNM, PA-BCI: Panama

This data package contains leaf mass data per unit area measured on a monthly basis from February to April, 2016, at the Bosque Protector San Lorenzo (PA-SLZ) and Parque Natural Metropolitano (PA-PNM) sites in Panama. Data from the Barro Colorado Island (PA-BCI) site are only available for March. This data was collected as part of the 2016 El Niño-Southern Oscillation (ENSO) campaign. Included in this data package are an Excel file with data (2016ENSO_Panama_LMA1) and two Excel files with associated metadata. Also included is a Word document (Metadata_description_2016_ENSO_Panama) with details such as data collection methods, equipment used, and site information. See related datasets for further sample details, leaf water potential, leaf spectra, gas exchange and leaf chemistry. VERSION 2 update. The identification of a species from the PNM site has been corrected as follows: the identification of the tree initially identified as Pseudosamanea guachapele (ALBIED) has been revised to Albizia adinocephala (ALBIAD). The updated data package includes revised data, metadata and protocol documents updated to reflect this change.

54 ENVIRONMENTAL SCIENCES↗

Leaf spectra, Feb2016-April2016, PA-SLZ, PA-PNM, PA-BCI: Panama

This data package contains leaf spectra data measured on a monthly basis from February to April, 2016. Measurements were taken at the Bosque Protector San Lorenzo (SLZ), Barro Colorado Island (BCI) and Parque Natural Metropolitano (PNM) NGEE Tropics sites in Panama. Data from the BCI site are only available for March, 2016. Within the attached zip file are PDF manuals for instruments used, a guide to data collection protocol, and metadata files, including a PDF containing metadata for the 2016 ENSO gas exchange campaign. Also included is an additional zip file "2016_ENSO_BNL_Leaf_Spectra_Archive.zip" with data in .csv format organized by site. This data was collected as part of the 2016 ENSO campaign. See related datasets (existing and future) for further sample details, leaf water potential data, LMA, and gas exchange and leaf chemistry data. VERSION 2 update. The identification of a species from the PNM site has been corrected as follows: the identification of the tree initially identified as Pseudosamanea guachapele (ALBIED) has been revised to Albizia adinocephala (ALBIAD). The updated data package includes revised data, metadata and protocol documents updated to reflect this change.

54 ENVIRONMENTAL SCIENCES↗

Precision Gas System Isotope Analyzer (PGSISO) Instrument Handbook

The PGSISO is a combination of several systems in series; (1) gas processing components that pressurize and prevent liquid water entering the sample stream, and (2) the Spectronus FTIR spectrometer, which measures continuous CO 2 , 12 CO 2 , 13 CO 2 , CH 4 , CO, N 2 O, and H 2 O. The Spectronus analyzer has been developed by the Centre for Atmospheric Chemistry at the University of Wollongong, Australia, and manufactured by Ecotech Pty Ltd, headquartered in Melbourne, Australia.

54 ENVIRONMENTAL SCIENCES↗

An Evaluation of a Neutron Time Correlated Interrogation Method for Measurement of Fissile Content in Research Reactor Spent Fuel Assemblies

There are many research reactors worldwide that have been, or are being converted from the use of high enrichment uranium (HEU) to low enrichment uranium (LEU, < 20% enriched). The verification of fissile content and initial enrichment of the spent fuel is needed for the effective safeguards of the fuel. The advanced experimental fuel counter (AEFC) was developed for the measurement of spent fuel rods and assemblies from research reactors for safeguards verification. This measurement system contains components for active neutron interrogation, passive neutron totals counting, neutron coincidence counting, and gross gamma-ray counting. This report presents the first application of the time correlated interrogation technique for the measurement of the 235 U content in research reactor spent fuel assemblies. The technique, called time correlated induced fission (TCIF), uses a 252 Cf neutron source to irradiate the fuel assembly, and the subsequent induced fission events in the fissile material are measured by coincidence counting. The doubles rates are enhanced by having the neutron trigger events from both the 252 Cf source and the induced fission neutrons in the same time gate in the coincidence analysis. The average neutrons per fission of the 252 Cf source is 3.76 and the induced fission neutrons for 235 U is 2.44, so the number of neutrons that are produced is higher than for random neutron interrogation. This high effective neutron number increases the multiplicity counting rates and reduces the statistical error. The background coincidence counts from the 252 Cf are reduced by the water in the sample cavity and the polyethylene surrounding the 3 He detector tubes. This method of active neutron interrogation has been applied to the measurement of spent research reactor (IRT) fuel assemblies. The advanced experimental fuel counter (AEFC) was used to compare the TCIF method with the typically used AmLi neutron interrogation source that emits neutrons that are random in time. The statistical uncertainty for the use of the random neutron source (AmLi) and the time correlated source ( 252 Cf) for spent fuel interrogations was evaluated.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Status Update on the High Precision Isotopic Measurements on High Burnup LWR Fuel in 2020

The US Department of Energy (DOE) Office of Nuclear Energy (NE) is currently investigating the feasibility of directly disposing dual-purpose (storage and transportation) canisters (DPCs) in a spent nuclear fuel (SNF) repository. Criticality during the repository performance period (10,000 years or more) is one of the major concerns related to direct disposal of DPCs, specifically as the system undergoes degradation in the repository environment and timeframe. Oak Ridge National Laboratory (ORNL) is developing an as-loaded criticality analysis methodology using full (actinides + fission products) burnup credit that exploits the inherent criticality margin associated with actual canister-specific loading configuration. Burnup credit criticality analysis requires validation of the depletion/decay codes used to generate the burned isotopic inventory of an assembly by comparing the code-predicted inventory with experimentally determined isotopic data. Currently, isotopic measurement data for boiling water reactors (BWR) SNF are limited, and additional measurements will be highly beneficial for BWR burnup credit analysis, which is essential to demonstrate disposability of BWR DPCs. Moreover, new pressurized water reactor (PWR) samples of isotopic measurements will expand the PWR sample population and consequently will greatly improve sample statistics. In turn, this will reduce uncertainty in the computational determination of the isotopic composition of commercial SNF and eliminate additional penalties currently used for lack of data. As part of the isotopic analysis task, eight diverse, high burnup (HBU) samples from several PWR rods are being dissolved and isotopically analyzed to provide high-quality measurement data for PWR SNF to reducing the uncertainties associated with PWR isotopic depletion validation. The isotopics of interest focus on nuclides important to burnup credit, shielding, and decay heat in PWR SNF. Additionally, eight high burnup BWR fuel samples from the Limerick nuclear power plant have been identified for measurement to support reducing uncertainties associated with BWR isotopic depletion validation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

2019 Groundwater Monitoring Report Project Shoal Area: Subsurface Corrective Action Unit 447

The Project Shoal Area is a site in Nevada where an underground nuclear test was conducted in 1963. It later came to be known as the Shoal, Nevada, Site. Surface contamination at the site has been remediated, but investigation of groundwater contamination resulting from the test is still in the corrective action process. Annual sampling and water-level monitoring are conducted as part of the subsurface corrective action strategy, which has focused on revising the site conceptual model and evaluating the adequacy of the monitoring well network. It has also included enhancements to the monitoring well network to address uncertainties in the groundwater flow direction and the cause of rising water levels in site wells west of the shear zone since the first hydrologic characterization (HC) wells were installed in 1996. Revisions to the site conceptual model and enhancements to the monitoring strategy were provided to Nevada Division of Environmental Protection (NDEP) in the Addendum to: Corrective Action Decision Document/Corrective Action Plan (CADD/CAP) for the Subsurface Corrective Action Unit 447 Shoal, Nevada, Site. NDEP approved the addendum to the CADD/CAP, which included an expanded contaminant boundary and compliance boundary for the site.

54 ENVIRONMENTAL SCIENCES↗

In-situ measurement of moist flue gas under high pressure using a nafion dryer and FTIR

The formation of the main flue gas species (NOx, SOx, CO2, and CO) in pressurized oxy-fuel combustion can be fundamentally different from oxy-fuel combustion at atmospheric pressure. To accurately obtain the concentration of these gas species in a pressurized oxy-fuel combustor, a gas measurement which maintains the sampling pressure is needed. Very few published studies have accomplished this, and never under the conditions reported herein. In this work, we fire PRB coal in a 100 kWth staged pressurized oxy-fuel combustor (SPOC) under a pressure 15 bara. We utilize a state-of-the-art FTIR (Thermo Scientific Nicolet iS20) with a novel high-pressure gas cell that is under process pressure to measure the in-situ flue-gas concentration in a sampled flow. However, water vapor can significantly interfere with the FTIR measurement, particularly under pressure. To address this problem, we have developed a high-pressure nafion dryer to selectively remove the water vapor from the flue gas while retaining the flue gas species. This approach can significantly increase the signal-noise ratio for the FTIR. By integrating the nafion dryer and the high-pressure gas cell, we were able to successfully measure flue gas species at system pressure with the FTIR.

Cheng, Mao↗

Non-destructive, in-situ evaluation of water presence using thermal contrast and cooled detector

Exemplary systems for detecting water include: a light source positioned to transmit thermal radiation through a sample; a lens assembly positioned to: receive the thermal radiation transmitted through the sample; and focus the transmitted thermal radiation onto a filter positioned between the lens assembly and a detector; and a cooling subsystem for cooling the filter and the detector to a temperature below that of the sample. Methods for detecting presence of water in a sample are also disclosed.

47 OTHER INSTRUMENTATION↗

Molecular detection of per- and polyfluoroalkyl substances in water using time-of-flight secondary ion mass spectrometry

Detection of per- and polyfluoroalkyl substances (PFASs) is crucial in environmental mitigation and remediation of these persistent pollutants. We demonstrate that time-of-flight secondary ion mass spectrometry (ToF-SIMS) is a viable technique to analyze and identify these substances at parts per trillion (ppt) level in real field samples without complicated sample preparation due to its superior surface sensitivity. Several representative PFAS compounds, such as perfluorooctanesulfonic acid (PFOS), perfluorobutanoic acid (PFBA), perfluoropentanoic acid (PFPeA), perfluoheptanoic acid (PFHpA), and perfluorononanoic acid (PFNA), and real-world groundwater samples collected from monitoring wells installed around at a municipal wastewater treatment plant located in Southern California were analyzed in this work. ToF-SIMS spectral comparison depicts sensitive identification of pseudo-molecular ions, characteristic of reference PFASs. Additionally, principal component analysis (PCA) shows clear discrimination among real samples and reference compounds. Our results show that characteristic molecular ion and fragments peaks can be used to identify PFASs. Furthermore, SIMS two-dimensional (2D) images directly exhibit the distribution of perfluorocarboxylic acid (PFCA) and PFOS in simulated mixtures and real wastewater samples. Such findings indicate that ToF-SIMS is useable to determine PFAS compounds in complex environmental water samples. In conclusion, ToF-SIMS provides simple sample preparation and high sensitivity in mass spectral imaging, offering an alternative solution for environmental forensic analysis of PFASs in wastewater in the future.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Surface Water Disinfection Byproducts and Organic Matter Characterization Data Associated with: “Disinfection byproducts formed during drinking water treatment reveal an export control point for dissolved organic matter in a subalpine headwater stream”

This dataset is associated with the publication “Disinfection byproducts formed during drinking water treatment reveal an export control point for dissolved organic matter in a subalpine headwater stream” published in Water Research X (Leonard et al. 2022; https://doi.org/10.1016/j.wroa.2022.100144). The associated study analyzed temporal trends from the Town of Crested Butte water treatment facility and synoptic sampling at Coal Creek in Crested Butte, Colorado, US. This work demonstrates how drinking water quality archives combined with synoptic sampling and targeted analyses can be used to identify and understand export control points for dissolved organic matter. This dataset is comprised of one main data folder containing (1) file-level metadata; (2) data dictionary; (3) metadata and international geo-sample number (IGSN) mapping file; (4) dissolved organic carbon (DOC), ultraviolet absorbance at 254 nanometers (UV254), total nitrogen (TN), and specific ultraviolet absorbance (SUVA) data; (5) disinfection bioproduct formation potential (DBP-FP) data; (6) readme; (7) methods codes; (8) water collection protocol; (9) folder of high resolution characterization of organic matter via 12 Tesla Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) through the Environmental Molecular Sciences Laboratory (EMSL; https://www.pnnl.gov/environmental-molecular-sciences-laboratory); and (10) folder of excitation emissions matrix (EEM) spectra. The FTICR folder contains a file of DOC (measured as non-purgeable organic carbon; NPOC) used for FTICR sample preparation. The FTICR folder also contains three subfolders: one subfolder containing the raw .xml data files, one containing the processed data, and the other containing instructions for using Formularity (https://omics.pnl.gov/software/formularity) and an R script to process the data based on the user's specific needs. All files are .csv, .pdf, .dat, .R, .ref, or .xml

54 ENVIRONMENTAL SCIENCES↗