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All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Organic contamination detection for isotopic analysis of water by laser spectroscopy

Hydrogen and oxygen stable isotope ratios (δ 2 H, δ 17 O, and δ 18 O values) are commonly used tracers of water. These ratios can be measured by isotope ratio infrared spectroscopy (IRIS). However, IRIS approaches are prone to errors induced by organic compounds present in plant, soil, and natural water samples. A novel approach using 17 O-excess values has shown promise for flagging spectrally contaminated plant samples during IRIS analysis. A systematic assessment of this flagging system is needed to prove it useful. Errors induced by methanol and ethanol water mixtures on measured IRIS and isotope ratio mass spectrometry (IRMS) results were evaluated. For IRIS analyses both liquid- and vapour-mode (via direct vapour equilibration) methods are used. The δ 2 H, δ 17 O, and δ 18 O values were measured and compared with known reference values to determine the errors induced by methanol and ethanol contamination. In addition, the 17 O-excess contamination detection approach was tested. This is a post-processing detection tool for both liquid and vapour IRIS triple-isotope analyses, utilizing calculated 17 O-excess values to flag contaminated samples. Organic contamination induced significant errors in IRIS results, not seen in IRMS results. Methanol caused larger errors than ethanol. Results from vapour-IRIS analyses had larger errors than those from liquid-IRIS analyses. The 17 O-excess approach identified methanol driven error in liquid- and vapour-mode IRIS samples at levels where isotope results became unacceptably erroneous. For ethanol contaminated samples, a mix of erroneous and correct flagging occurred with the 17 O-excess method. Here our results indicate that methanol is the more problematic contaminant for data corruption. The 17 O-excess method was therefore useful for data quality control. Organic contamination caused significant errors in IRIS stable isotope results. These errors were larger during vapour analyses than during liquid IRIS analyses, and larger for methanol than ethanol contamination. The 17 O-excess method is highly sensitive for detecting narrowband (methanol) contamination error in vapour and liquid analysis modes in IRIS.

60 APPLIED LIFE SCIENCES↗
NASA NTRS1998

A Data Base of Nutrient Use, Water Use, CO2 Exchange, and Ethylene Production by Soybeans in a Controlled Environment

A data set is given describing daily nutrient and water uptake, carbon dioxide (CO2) exchange, ethylene production, and carbon and nutrient partitioning from a 20 sq m stand of soybeans (Glycine max (L.) Merr. cv. McCall] for use in bioregenerative life support systems. Stand CO2 exchange rates were determined from nocturnal increases in CO2 (respiration) and morning drawdowns (net photosynthesis) to a set point of 1000 micromol/ mol each day (i.e., a closed system approach). Atmospheric samples were analyzed throughout growth for ethylene using gas chromatography with photoionization detection (GC/PH)). Water use was monitored by condensate production from the humidity control system, as well as water uptake from the nutrient solution reservoirs each day. Nutrient uptake data were determined from daily additions of stock solution and acid to maintain an EC of 0.12 S/m and pH of 5.8. Dry mass yields of seeds, pods (without seeds), leaves, stems, and roots are provided, as well as elemental and proximate nutritional compositions of the tissues. A methods section is included to qualify any assumptions that might be required for the use of the data in plant growth models, along with a daily event calendar documenting set point adjustments and the occasional equipment or sensor failure.

Wheeler, R. M.↗
DOE OSTI2024

Detection and Screening of Organic Contaminants in A Riverine System of Georgia Using Non-Targeted Analysis

Numerous organic chemicals exist within aquatic environments, yet effectively screening and prioritizing them is a huge challenge. This study provides a comprehensive investigation into the ecological dynamics of the North Oconee River within Athens-Clarke County, Georgia, with a specific focus on the distribution of 33 identified compounds, including a prominent pesticide. The research, conducted in the riverine ecosystems proximal to the Firefly trail, employs advanced analytical techniques to elucidate potential contamination sources arising from agricultural and urban runoff. Intriguingly, the study reveals North Oconee River near the Firefly Trail as a notable site for heightened pesticide contamination, warranting a meticulous exploration of its origins. Furthermore, the investigation unveils the intricate microbial degradation processes of malathion within the North Oconee River, elucidating the pivotal role played by microbial activity in river water. The detection of degradant byproducts prompts the considerations of bioavailability and toxicity, associating potential implications for the river’s overall ecological health. Ongoing research endeavors to precisely quantify environmental risks and unravel indigenous microbial degradation pathways, presenting pivotal contributions to the scientific community’s understanding of complex riverine ecosystems. This research serves as a foundational piece in informing sustainable environmental management practices and emphasizes the urgency of comprehensive stewardship in safeguarding aquatic ecosystems.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1988

Hydrometeor development in cold clouds in FIRE

The microphysical characteristics of cold clouds were examined using aircraft. The clouds investigated ranged in temperature from minus 20 to minus 46 C. Liquid water was detected in these clouds at minus 35 C and may exist at even colder temperatures. Aircraft patterns in the form of Lagrangian spirals were used to interpret particle growth processes. Significant broadening of the particle size spectra is observed with minor changes in the spectra at small sizes. Virtually all of the broadening observed is attributable to ice particle aggregation which occurs at all temperatures. The crystals comprising the aggregates are of comparable size, joined either at tips or edges, and are usually 2 in number at temperatures lower than minus 25 C, increasing to 3 or more at warmer temperatures. The data strongly suggest that sintering is the mechanism through which the crystals aggregate. Aggregation appears to be important in the transfer of water mass from upper to lower levels in clouds.

Heymsfield, Andrew J.↗
NASA NTRS1993

Temporal changes in endmember abundances, liquid water and water vapor over vegetation at Jasper Ridge

Imaging spectrometry offers a new way of deriving ecological information about vegetation communities from remote sensing. Applications include derivation of canopy chemistry, measurement of column atmospheric water vapor and liquid water, improved detectability of materials, more accurate estimation of green vegetation cover and discrimination of spectrally distinct green leaf, non-photosynthetic vegetation (NPV: litter, wood, bark, etc.) and shade spectra associated with different vegetation communities. Much of our emphasis has been on interpreting Airborne Visible/Infrared Imaging Spectrometry (AVIRIS) data spectral mixtures. Two approaches have been used, simple models, where the data are treated as a mixture of 3 to 4 laboratory/field measured spectra, known as reference endmembers (EM's), applied uniformly to the whole image, to more complex models where both the number of EM's and the types of EM's vary on a per-pixel basis. Where simple models are applied, materials, such as NPV, which are spectrally similar to soils, can be discriminated on the basis of residual spectra. One key aspect is that the data are calibrated to reflectance and modeled as mixtures of reference EM's, permitting temporal comparison of EM fractions, independent of scene location or data type. In previous studies the calibration was performed using a modified-empirical line calibration, assuming a uniform atmosphere across the scene. In this study, a Modtran-based calibration approach was used to map liquid water and atmospheric water vapor and retrieve surface reflectance from three AVIRIS scenes acquired in 1992 over the Jasper Ridge Biological Preserve. The data were acquired on June 2nd, September 4th and October 6th. Reflectance images were analyzed as spectral mixtures of reference EM's using a simple 4 EM model. Atmospheric water vapor derived from Modtran was compared to elevation, and community type. Liquid water was compare to the abundance of NPV, Shade and Green Vegetation (VG) for select sites to determine whether a relationship existed, and under what conditions the relationship broke down. Temporal trends in endmember fractions, liquid water and atmospheric water vapor were investigated also. The combination of spectral mixture analysis and the Modtran based atmospheric/liquid water models was used to develop a unique vegetation community description.

Roberts, Dar A.↗
NASA NTRS2005

Nighttime Cirrus Detection using Atmospheric Infrared Sounder Window Channels and Total Column Water Vapor

A method of cirrus detection at nighttime is presented that utilizes 3.8 and 10.4 (micro)m infrared (IR) window brightness temperature differences (dBT) and total column precipitable water (PW) measurements. This technique is applied to the Atmospheric Infrared Sounder (AIRS) and Advanced Microwave Sounding Unit A (AMSU-A) instrument suite on board EOS-Aqua, where dBT is determined from sets of carefully selected AIRS window channels, while PW is derived from the synergistic AIRS and AMSU-A water vapor retrievals. Simulated and observed dBT for a particular value of PW are not constant; several physical factors impact dBT, including the variability in temperature and relative humidity profiles, surface emissivity, instrument noise, and skin/ near-surface air temperature differences. We simulate clear-sky dBT over a realistic range of PWs using 8350 radiosondes that have varying temperature and relative humidity profiles. Thresholds between cloudy and uncertain sky conditions are derived once the scatter in the clear-sky dBT is determined. Simulations of optically thin cirrus indicate that this technique is most sensitive to cirrus optical depth in the 10 (micro)m window of 0.1-0.15 or greater over the tropical and subtropical oceans, where surface emissivity and skin/near-surface air temperature impacts on the IR radiances are minimal. The method at present is generally valid over oceanic regions only, specifically, the tropics and subtropics. The detection of thin cirrus, and other cloud types, is validated using observations at the Atmospheric Radiation Measurement (ARM) program site located at Manus Island in the tropical western Pacific for 89 coincident EOS-Aqua overpasses. Even though the emphasis of this work is on the detection of thin cirrus at nighttime, this technique is sensitive to a broad cloud morphology. The cloud detection technique agrees with ARM-detected clouds 82-84% of the time, which include thin cirrus, as well as other cloud types. Most of the disagreements are well explained by AIRS footprint-scale heterogeneity compared to ARM point measurements, cirrus overlying lower-layer water clouds, possible mixed phase microphysics in midlevel clouds, and significant IR channel noise for cold BT scenes over deep convective towers.

Atmospheric Radiation Measurement (RAM)↗
NASA NTRS2022

Environmental Testing of the OVEN System for Lunar Water Extraction and Prospecting

Introduction: The presence of water ice in permanently shadowed regions on the lunar surface [1] may enable a sustained human presence on the Moon with minimal need for consumables. However, in order to develop a long term utilization plan that includes the usage of in-situ water we must first understand the abundance, stratigraphy and distribution of this re-source. Multiple space agencies currently have plans for lunar water prospecting missions. The Optimized Volatile Extraction Node (OVEN) was designed for water prospecting missions that require samples to be weighed, sealed, and heated as the means of determining water concentration. This method of water quantification necessitates a fair amount of automation, so a rigorous environmental test program was performed in order to build confidence in the performance of the OVEN design. The work presented here describes the OVEN environmental test program as well as ongoing efforts to improve on the design. Vibration: The OVEN participated in two rounds of random vibration tests. The first test was a stand-alone test performed at the Energy Systems Test Area of the Johnson Space Center. The second test was an integrated test with the mobile platform developed for the Resource Prospector project. The OVEN survived both tests without damage, but the tests did provide valuable lessons learned with regards to specific operations. Thermal Vacuum: The OVEN was successfully demonstrated at a temperature range of -50 to 75 C in a thermal vacuum chamber. The need to heat motor gearboxes at lower temperatures was predetermined so this test program was completed by implementing a method of gearbox heating that used the existing circuitry within the motors. Dust: A custom dynamometer was built in order to determine the torque required to move the various mechanisms within the OVEN at a range of temperatures. The OVEN system was coated with lunar dust simulant in order to determine mechanism torques under a worst-case operating condition. Sublimation: Sublimation losses within the OVEN were quantified through a series of test configurations, including an integrated test in a thermal vacuum chamber at Glenn Research Center [2]. Current Work: The OVEN subsystem is currently not a component of any existing prospecting missions, but work continues that will take the lessons learned from previous environmental tests and improve on the design in order to be considered for future prospecting opportunities. References: [1] Colaprete, A., Schultz, P., Heldmann, J., Wooden, D., Shirley, M., Ennico, K., ... & Sollitt, L. (2010). Detection of water in the LCROSS ejecta plume. science, 330(6003), 463-468. [2] Kleinhenz, J., Smith, J., Roush, T., Colaprete, A., Zacny, K., Paulsen, G., ... & Paz, A. (2018). Volatiles Loss from water bearing regolith simulant at Lunar Environments. In Earth and Space 2018: Engineering for Extreme Environments (pp. 454-466). Reston, VA: American Society of Civil Engineers.

A Paz↗
DOE OSTI2023

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↗
DOE OSTI2021

Molecular Engineering of 2D Nanomaterial Field-Effect Transistor Sensors: Fundamentals and Translation across Innovation Spectrum

We report over the last decade, 2D layered nanomaterials have attracted significant attention across the scientific community due to their rich and exotic properties. Various nanoelectronic devices based on these 2D nanomaterials have been explored and demonstrated, including those for environmental applications. Here, the fundamental attributes of 2D layered nanomaterials for field-effect transistor (FET) sensors and tunneling FET (TFET) sensors, which provide versatile detection of water contaminants such as heavy-metal ions, bacteria, nutrients, and organic pollutants, are discussed. The major challenges and opportunities are also outlined for designing and fabricating 2D nanomaterial FET/TFET sensors with superior performance. Translation of these FET/TFET sensors from fundamental research to applied technology is illustrated through a case study on graphene-based real-time FET water sensors. A second case study centers on large-scale sensor networks for water-quality monitoring to enable intelligent drinking water and river-water systems. Overall, 2D nanomaterial FET sensors have significant potential for enabling a human-centered intelligent water system that can likely be applied to other precarious water supplies around the globe.

2D nanomaterials↗
DOE OSTI2026

Coupling geophysical, geological, geochemical and mineralogical assessments to examine preferential contaminant transport pathways in interbedded fractured bedrock

This study shows that a multi-faceted approach, combining borehole geophysical logging and surface seismic P-wave first-arrival tomography with confirmatory coring, well installation, and chemical and mineralogical analysis, is effective for identifying difficult-to-locate preferential contaminant transport pathways in deeper fractured bedrock. Seismic tomography detected porous 10–20 m wide elongated fractured conduits that allow acidic groundwater contaminated with uranium (U) and nitrate (NO 3 - ) to migrate within interbedded shale-limestone bedrock over 1000 m from a former disposal facility (S-3 Ponds site) located at the DOE Y-12 National Security Complex in Tennessee (USA). Conventional drilling techniques would easily miss these conduits because they are oriented parallel with fractured bedding planes. Synchrotron analysis of aquifer solids revealed that > 95 % of the U is hexavalent (U VI ). This uranyl (UO 2 2+ ) species is coordinated with carbonate, iron oxide, silicate and phosphate minerals within cemented white to yellow precipitates, which contain U concentrations as high as ∼21.6 % by weight fraction. Identifying the presence of these mineral phases, enables a further understanding of the potential effectiveness of remediation actions. The combination of methodologies presented here can also be applied to other explorations, such as the detection of water supply.

Fate and transport↗
DOE OSTI2020

Functional metal–organic frameworks as effective sensors of gases and volatile compounds

Developing efficient sensor materials with superior performance for selective, fast and sensitive detection of gases and volatile organic compounds (VOCs) is essential for human health and environmental protection, through monitoring indoor and outdoor air pollutions, managing industrial processes, controlling food quality and assisting early diagnosis of diseases. Metal–organic frameworks (MOFs) are a unique type of crystalline and porous solid material constructed from metal nodes (metal ions or clusters) and functional organic ligands. They have been investigated extensively for possible use as high performance sensors for the detection of many different gases and VOCs in recent years, due to their large surface area, tunable pore size, functionalizable sites and intriguing properties, such as electrical conductivity, magnetism, ferroelectricity, luminescence and chromism. The high porosity of MOFs allows them to interact strongly with various analytes, including gases and VOCs, thus resulting in easily measurable responses to different physicochemical parameters. Although much of the recent work on MOF-based luminescent sensors have been summarized in several excellent reviews (up to 2018), a comprehensive overview of these materials for sensing gases and VOCs based on chemiresistive, magnetic, ferroelectric, and colorimertic mechanisms is missing. In this review, we highlight the most recent progress in developing MOF sensing and switching materials with an emphasis on sensing mechanisms based on electricity, magnetism, ferroelectricity and chromism. We provide a comprehensive analysis on the MOF–analyte interactions in these processes, which play a key role in the sensing performance of the MOF-based sensors and switches. We discuss in detail possible applications of MOF-based sensing and switching materials in detecting oxygen, water vapor, toxic industrial gases (such as hydrogen sulfide, ammonia, sulfur dioxide, nitrous oxide, carbon oxides and carbon disulfide) and VOCs (such as aromatic and aliphatic hydrocarbons, ketones, alcohols, aldehydes, chlorinated hydrocarbons and N,N'-dimethylformamide). Altogether, this review serves as a timely source of information and provides insight for the future development of advanced MOF materials as next-generation gas and VOC sensors.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Low energy neutrino detection with a compact water-based liquid scintillator detector

In this study, the conceptual design and physics simulations of a near-field Water-based Liquid Scintillator (WbLS) detector placed 100 m from the Akkuyu Nuclear Power Plant (ANPP), currently under construction and aiming at being Turkey’s first nuclear power plant, is presented. The ANPP is an excellent opportunity for neutrino studies and the development of an R &D program for neutrino detectors in Turkey. The Reactor Neutrino Experiments of Turkey (RNET) program includes a compact detector with a 2.5-ton volume of WbLS and a ~ 30% photo-coverage, and the program is planned to be expanded with a medium-size 30-ton detector that will be an international testbed for WbLS and new detector technologies through low energy neutrino studies. In the following, the focus will be on the smaller ~2.5 ton detector, instrumented with 8-in. high quantum efficiency PMTs and two layers of cosmic veto paddles, covering all sides of the detector, to track and veto cosmic particles. Inverse Beta Decay (IBD) events from electron anti-neutrinos generated in the reactor core are simulated using the RAT-PAC simulation package and several liquids with different percentages of Liquid Scintillator (LS) and Gadolinium (Gd) are investigated.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2020

Survey of Technologies to Meet PAG limits for Detection of Cesium-137 in Water

The goal of this report is to evaluate the process of adding a sorbent to the sampling process to preconcentrate Cs-137 and then analyze the sorbent to provide a rapid assessment of results to guide decisions on drinking water sources and the protection of the public. Multiple unit design variables were considered: sample configuration/geometry, sorbent efficiency, sample volume. Model simulations demonstrated through these unit design efficiencies that 10 L of sample volume processed through a sorbent provides nearly two orders of magnitude improvement in sample counting time to provide results to a decision maker than the current process. Over 60 publications and reports concerning Cs-137 and sorbents were evaluated. The key attributes were readiness of sorbent to be deployed in a mobile laboratory environment, and minimum sample preparation and conditioning. Examples of sorbents not considered further included nanomaterials, which have not been evaluated at a commercial scale and are limited in availability. The recommended sorbents for further consideration include: ferrocyanide salts, zeolite, and chemically modified granular activated carbon.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Using Atmospheric Inverse Modelling of Methane Budgets with Copernicus Land Water and Wetness Data to Detect Land Use-Related Emissions

Climate change mitigation requires countries to report their annual greenhouse gas (GHG) emissions and sinks, including those from land use, land use change, and forestry (LULUCF). In Finland, the LULUCF sector plays a crucial role in achieving net-zero GHG emissions, as the sector is expected to be a net sink. However, accurate estimates of LULUCF-related GHG emissions, such as methane (CH 4 ), remain challenging. We estimated LULUCF-related CH 4 emissions in Finland in 2013–2020 by combining national land cover and remote-sensed surface wetness data with CH 4 emissions estimated by an inversion model. According to our inversion model, most of Finland’s CH 4 emissions were attributed to natural sources such as open pristine peatlands. However, our research indicated that forests with thin tree cover surrounding open peatlands may also be a significant source of CH 4 . Unlike open pristine peatlands and pristine peatlands with thin tree cover, surrounding transient forests are included in the Finnish GHG inventory if they meet the criteria used for forest land. The current Finnish national GHG inventory may therefore underestimate CH 4 emissions from forested organic soils surrounding open peatlands, although more precise methods and data are needed to verify this. Given the potential impact on net GHG emissions, CH 4 emissions from transitional forests on organic soils should be further investigated. Furthermore, the results demonstrate the potential of combining atmospheric inversion modelling of GHGs with diverse data sources and highlight the need for methods to more easily combine atmospheric inversions with national GHG inventories.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

TeV Emission of Galactic Plane Sources with HAWC and H.E.S.S.

The High Altitude Water Cherenkov (HAWC) observatory and the High Energy Stereoscopic System (H.E.S.S.) are two leading instruments in the ground-based very-high-energy γ-ray domain. HAWC employs the water Cherenkov detection (WCD) technique, while H.E.S.S. is an array of Imaging Atmospheric Cherenkov Telescopes (IACTs). The two facilities therefore differ in multiple aspects, including their observation strategy, the size of their field of view, and their angular resolution, leading to different analysis approaches. Until now, it has been unclear if the results of observations by both types of instruments are consistent: several of the recently discovered HAWC sources have been followed up by IACTs, resulting in a confirmed detection only in a minority of cases. With this paper, we go further and try to resolve the tensions between previous results by performing a new analysis of the H.E.S.S. Galactic plane survey data, applying an analysis technique comparable between H.E.S.S. and HAWC. Events above 1 TeV are selected for both data sets, the point-spread function of H.E.S.S. is broadened to approach that of HAWC, and a similar background estimation method is used. This is the first detailed comparison of the Galactic plane observed by both instruments. H.E.S.S. can confirm the γ-ray emission of four HAWC sources among seven previously undetected by IACTs, while the three others have measured fluxes below the sensitivity of the H.E.S.S. data set. Remaining differences in the overall γ-ray flux can be explained by the systematic uncertainties. Therefore, we confirm a consistent view of the γ-ray sky between WCD and IACT techniques.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1975

The use of lasers for hydrographic studies

The utilization of remote laser sensors in water pollution detection and identification, coastal environmental monitoring, and bathymetric depth sounding, is discussed. qr

Kim, H. H.↗