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All sourcesNASA NTRSDOE OSTI
NASA NTRS1999

Instrumentation Working Group Summary

The Instrumentation Working Group compiled a summary of measurement techniques applicable to gas turbine engine aerosol precursors and particulates. An assessment was made of the limits, accuracy, applicability, and technology readiness of the various techniques. Despite advances made in emissions characterization of aircraft engines, uncertainties still exist in the mechanisms by which aerosols and particulates are produced in the near-field engine exhaust. To adequately assess current understanding of the formation of sulfuric acid aerosols in the exhaust plumes of gas turbine engines, measurements are required to determine the degree and importance of sulfur oxidation in the turbine and at the engine exit. Ideally, concentrations of all sulfur species would be acquired, with emphasis on SO2 and SO3. Numerous options exist for extractive and non-extractive measurement of SO2 at the engine exit, most of which are well developed. SO2 measurements should be performed first to place an upper bound on the percentage of SO2 oxidation. If extractive and non-extractive techniques indicate that a large amount of the fuel sulfur is not detected as SO2, then efforts are needed to improve techniques for SO3 measurements. Additional work will be required to account for the fuel sulfur in the engine exhaust. Chemical Ionization Mass Spectrometry (CI-MS) measurements need to be pursued, although a careful assessment needs to be made of the sampling line impact on the extracted sample composition. Efforts should also be placed on implementing non-intrusive techniques and extending their capabilities by maximizing exhaust coverage for line-of-sight measurements, as well as development of 2-D techniques, where feasible. Recommendations were made to continue engine exit and combustor measurements of particulates. Particulate measurements should include particle size distribution, mass fraction, hydration properties, and volatile fraction. However, methods to ensure that unaltered samples are obtained need to be developed. Particulate speciation was also assigned a high priority for quantifying the fractions of carbon soot, PAH, refractory materials, metals, sulfates, and nitrates. High priority was also placed on performing a comparison of particle sizing instruments. Concern was expressed by the workshop attendees who routinely make particulate measurements about the variation in number density measured during in-flight tests by different instruments. In some cases, measurements performed by different groups of researchers during the same flight tests showed an order of magnitude variation. Second priority was assigned to measuring concentrations of odd hydrogen and oxidizing species. Since OH, HO2, H2O2, and O are extremely reactive, non-extractive measurements are recommended. A combination of absorption and fluorescence is anticipated to be effective for OH measurements in the combustor and at the engine exit. Extractive measurements of HO2 have been made in the stratosphere, where the ambient level of OH is relatively low. Use of techniques that convert HO2 to OH for combustor and engine exit measurements needs to be evaluated, since the ratio of HO2/OH may be 1% or less at both the combustor and engine exit. CI-MS might be a viable option for H2O2, subject to sampling line conversion issues. However, H2O2 is a low priority oxidizing species in the combustor and at the engine exit. Two candidates for atomic oxygen measurements are Resonance Enhanced Multi-Photon Ionization (REMPI) and Laser-Induced Fluorescence (LIF). Particulate measurement by simultaneous extractive and non-extractive techniques was given equal priority to the oxidizer measurements. Concern was expressed over the ability of typical ground test sampling lines to deliver an unaltered sample to a remotely located instrument. It was suggested that the sampling probe and line losses be checked out by attempting measurements using an optical or non-extractive technique immediately upstream of the sampling probe. This is a possible application for Laser Induced Incandescence (LII) as a check on the volume fraction of soot. Optical measurements of size distribution are not well developed for ultrafine particles less than about 20 nm in diameter, so a non-extractive technique for particulate size distribution cannot be recommended without further development. Carbon dioxide measurements need to be made to complement other extractive measurement techniques. CO2 measurements enable conversion of other species concentrations to emission indices. Carbon monoxide, which acts as a sink for oxidizing species, should be measured using non-extractive techniques. CO can be rapidly converted to CO2 in extractive probes, and a comparison between extractive and non-extractive measurements should be performed. Development of non-extractive techniques would help to assess the degree of CO conversion, and might be needed to improve the concentration measurement accuracy. Measurements of NO(x) will continue to be critical due to the role of NO and NO2 in atmospheric chemistry, and their influence on atmospheric ozone. Time-resolved measurements of temperature, velocity, and species concentrations were included on the list of desired measurement. Thermocouples are typically adequate for engine exit measurements. PIV and LDV are well established for obtaining velocity profiles. The techniques are listed in the accompanying table; are divided into extractive and non-extractive techniques. Efforts were made to include a measurement uncertainty for each technique. An assessment of the technology readiness was included.

Zaller, Michelle↗
NASA NTRS1978

Ultraviolet-photoproduced organic solids synthesized under simulated Jovian conditions - Molecular analysis

In an earlier paper, Khare and Sagan reported the production of a brownish polymeric material from the near-ultraviolet irradiation of simulated jovian atmospheres with a low hydrogen abundance. Examination of this product indicates that hydrogen sulfide is the initial photon acceptor; the powder resulting after extraction with benzene is 84 percent sulfur, largely S8. In results reported here, the remaining 16 percent was pyrolyzed and then examined by gas chromatography-mass spectrometry. Pyrolysis at 450 C yielded a series of alkanes, alkenes, C3-alkylbenzenes, aromatics, thiophenes, alkylthiophenes, alkylmercaptans, alkyldisulfides, together with the nitrogenous compounds hydrogen cyanide, methyl cyanide, alkylisothiocyanates, acrylonitrile, and allylisothiocyanates. Some of these compounds might be sought on Jupiter and Saturn and their satellites by remote infrared and ultraviolet spectroscopy and directly by entry probes.

Khare, B. N.↗
NASA NTRS2000

CCD-Based XRD/XRF for Determining Environmental Mineralogy on Mars

Health effects from Martian dusts will be a concern for any manned Mars missions. Nuisance dusts plagued the Apollo astronauts, but dusts of more hazardous mineralogy, in habitats occupied by Mars astronauts weakened by a long-duration mission, may be more than a nuisance. Chemical hazards in Martian regolith attributable to S, Cl, Br, Cd, and Pb are known or strongly suspected to be present, but terrestrial studies of the health effects of dusts indicate that accurate determination of mineralogy is a critical factor in evaluating inhalation hazards. Mineral inhalation hazards such as the Group-I carcinogenic zeolite erionite, which is demonstrated to cause mesothelioma, cannot be identified by chemical analysis alone. Studies of palagonite analogs raise the possibility that erionite may occur on Mars. In addition to health effects concerns, environmental mineralogy has significant importance in resource extraction, groundwater use, and sustained agriculture. The high sulfur and chlorine content of Martian regolith will affect all of these uses, but the nature of mineralogic reservoirs for S and Cl will determine their uptake and concentration in extracted groundwater and in agricultural applications of regolith. Wet chemistry experiments planned for the Mars Environmental Compatibility Assessment (MECA) will define some of the consequences of water/soil interaction, but an understanding of the mineralogic basis for water-rock reactions is needed to understand the mechanisms of reaction and to apply the results of a few experiments to larger scales and different conditions.

Vaniman, D. T.↗
DOE OSTI2020

Sulfur Pellets Responses to a Bare and Steel Reflected Pulse of the Oak Ridge National Laboratory Health Physics Research Reactor

The experiments analyzed in this report were conducted at the Health Physics Research Reactor (HPRR), also known as the $\textit{Fast Burst Reactor}$. The reactor was designed and built at Oak Ridge National Laboratory (ORNL) in 1961. The HPRR was an unmoderated, unshielded fast reactor that used highly enriched uranium and molybdenum alloy as fuel. The reactor was initially sent to the Nevada Test Site in 1962, where it was used to evaluate radiation doses received as a result of the Hiroshima and Nagasaki bombings during World War II. A few years later, the reactor was sent back to ORNL to be part of the Dosimetry Application Research (DOSAR) facility shown in Figure 1, which included a reactor building shown on the left (west) of the picture and a control and laboratory building in the upper right corner (northeast). The critical assembly was used for numerous technical studies, including systems calibration, dosimetry, radiobiology of plants and animals, testing of radiation alarms, as well as teaching and training in radiation dosimetry and nuclear engineering. Between 1963 and 1987, the HPRR was operated for thousands of hours, achieving criticality close to 10,000 times and motivating many publications. The HPRR was decommissioned in 1987. The goal of this effort was to use historical data from operation of the HPRR to create a criticality accident alarm system (CAAS) benchmark to be included in the $\textit{International Handbook of Evaluated Criticality Safety Benchmark Experiments}$ (ICSBEP Handbook). A thorough inspection was performed of all available documentation and information available. The most promising experiments that were selected for evaluation were those described in the 1987 ORNL report entitled $\textit{Health Physics Research Reactor Reference Dosimetry}$, ORNL-6240. The report includes reference dosimetry results of the shielded and unshielded configurations of the HPRR after burst operations. Because of changes to the reactor positioning and storage systems that were made in 1985, the previous dosimetry reports became obsolete, and the newly designed experiments were needed to create the HPRR’s adjusted dosimetry data. The various results reported in ORNL-6240 include reference doses and dose equivalents from different conventions at different distances and elevations as determined using the detected neutron fluence and conversion factors. The HPRR neutron fluence was obtained through different methods, including sulfur pellet analysis and threshold detector unit data. Information about the HPRR spectrum was also obtained through Bonner sphere measurements. This benchmark is focused on a part of the measured sulfur fluences reported in Appendix H of ORNL-6240. Standard commercial sulfur pellets were placed at different distances from the HPRR centerline during burst operation and were activated due to the 32 S(n,p) 32 P reaction. The resulting 32 P activity was then measured and the information about the corresponding sulfur fluence and/or neutron dose could be extracted. Many of those measurements have 7 been performed with the HPRR in its bare configuration or with different shields (combinations of Lucite, concrete, steel). All the necessary, precise information about material and/or dimensions of the different shields was not found, so it was decided to focus only on the unshielded and steel-shielded configurations to minimize the benchmark uncertainty. A total of 31 cases (24 unshielded and 7 shielded cases at different positions) of sulfur fluence were selected before evaluation to develop the benchmark.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2021

Hydrothermal Liquid Recovery of Rare Earth Elements and Critical Materials

This project demonstrated the technical viability of using tunable hydrothermal liquid (HTL) solutions to recover valuable minerals from a range of source materials. The effort focused upon rare earth elements (REE) and other minerals critical to the industrial security of the United States. This effort demonstrated, for the first time, that s, supercritical water (SCW) in particular, can: Extract critical and valuable minerals from a range of matrices ranging from rock ore to biomass; The process can be used to recover a wide range of minerals; This novel extraction chemistry can be cheap, simple, and nontoxic/”green”: The chemical extraction uses water, the cheapest industrial acid (sulfuric), and simple salts (i.e. sodium sulfate). However, other acids, salts, and additives could be used as appropriate. This Laboratory Directed Research and Development (LDRD) project identified that the process is complex with many interacting factors, but the benefits are significant if the complexities can be resolved. Challenges remain in the development of this technology and are described in this report. However, the results are positive, and commercial partners have already expressed interest. In summary, a novel, green, inexpensive mineral extraction process has been developed and demonstrated in a small batch reactor system. The effort provided information for an invention disclosure, proposal to DOE, and will support future business development efforts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2002

Thermococcus sulfurophilus sp. nov., a New Hyperthermophilic, Sulfur-Reducing Archaeon Isolated from Deep-Sea Hydrothermal Vent

A new hyperthermophilic, anaerobic, sulfur-reducing, organo-heterotrophic archaeon, strain OGL-20P, was isolated from "black smoker" chimney material at the Rainbow hydrothermal vent site in the Atlantic Ocean (36.2 N; 33.9 W). The cells of strain OGL-20P have irregular coccoid shape and are motile with a single flagellum. Growth occurs within pH range of 5.5-8.2 (optimal at pH 7.0-7.2), salinity range of 1-5% NaCl (optimal concentration 3% NaCl wt/vol), and temperature range of +55 C to +94 C (optimal growth at +83 C to +85 C). Strain OGL-20P is resistant to freezing (at -20 C). New isolate is strictly anaerobic with sulfur-type of respiration. A limited number of compounds are utilized as electron donors, including peptone, becto-tryptone, casamino-acids, and yeast extract but does not grow with separate amino acids. Sulfur and Iron can be used as electron acceptors; but not sulfate, sulfite, thiosulfate or nitrate. Strain OGL-20P is resistant to chloramphenicol, kanamycin, and gentamycin. Growth of str. OGL20P is inhibited by tetracyclin but not by Na2MoO4. The G+C content of DNA is 57.2 mol%. The 16S ribosomal RNA sequence analysis allows one to classify strain OGL-20P as a representative of a now species of Thermococcus genus. The name Thermococcus sulfurophilus op. nov., was suggested for the new isolate, type strain OGL-20P (sup T) (= ATCC BAA_394 (sup T) = DSM...(supT)).

Pikuta, Elena V.↗
NASA NTRS1996

Sulfur and Hydrogen Isotope Anomalies in Organic Compounds from the Murchison Meteorite

Isotopic measurements have been made on organic sulfur and phosphorus compounds recently discovered in the Murchison meteorite. Carbon, hydrogen and sulfur measurements were performed on individual members of the organic sulfur compounds, alkyl sulfonates; and carbon and hydrogen measurements were made on bulk alkyl phosphonates. Cooper and Chang reported the first carbon isotopic measurements of Murchison organic sulfonates, providing insight into the potential synthetic mechanisms of these and, possibly, other organic species. Hydrogen isotopic measurements of the sulforiates now reveal deuterium excesses ranging from +660 to +2730 %. The deuterium enrichments indicate formation of the hydrocarbon portion of these compounds in a low temperature astrophysical environment consistent with that of dense molecular clouds. Measurements of the sulfur isotopes provide further constraints on the origin and mechanism of formation of these organic molecules. Recently, there has been growing documentation of sulfur isotopic anomalies in meteoritic material. Thiemens and Jackson have shown that some bulk ureilites possess excess S-33 and Thiemens et al. have reported excess S-33 in an oldhamite separate from the Norton County meteorite. Rees and Thode reported a large S-33 excess in an Allende acid residue, however, attempts to verify this measurements have been unsuccessful, possibly due to the heterogeneous nature of the carrier phase. With the recognition that sulfur isotopes may reflect chemistry in the protosolar nebula or the precursor molecular cloud, identification of potential carriers is of considerable interest. In the present study, the stable isotopes of sulfur were measured in methane sulfonic acid extracted from the Murchison meteorite. The isotopic composition was found to be: (delta)S-33 = 2.48 %, (delta)S-34 = 2.49 % and (delta)S-36 = 6.76 %. Based upon analysis of more than 60 meteoritic and numerous terrestrial samples, the mass fractionation lines are defined by Delta-33 = (delta)S-33 -0.50(delta)S-34 and Delta-36 = (delta)s-36 - 1.97 (delta)S-34. From these relationships Delta-33 = 1.24 % and Delta-36 = 0.89 % are observed. These anomalies, particularly the Delta-33, lie well outside the range of analytical uncertainty. They are the largest observed in any meteoritic component and the first found in an organosulfur compound. As discussed by Thiemens and Jackson, due to it's position on the periodic chart, sulfur undergoes chemically induced mass independent isotopic fractionations as does oxygen. Experiments by Mauersberger et. al. show that in such processes, the magnitude of fractionation for the different isotopically substituted species varies with mass and angular momentum; thus, anomalies are expected for both S-33 and S-36, but not necessarily of the same magnitude. Laboratory experiments have also confirmed that chemically produced, mass independent fractionations are mediated by molecular symmetry factors. A chemical source of fractionation requires that the sulfur isotopic anomaly was established in the gas phase, probably in reactions involving symmetric CS2. The discovery of an anomalous sulfur isotopic composition in a specific molecule containing excess deuterium is an important advance in the understanding of the cosmochemistry of sulfur. This evidence suggests that methanesulfonic acid was synthesized by interstellar processes. Further measurements and details of possible synthesis and fractionation mechanisms will be presented.

Cooper, G. W.↗
NASA NTRS2006

Thiophenes as Indicators of Aqueous Alteration in Carbonaceous Meteorites

A common class of organic compound in low petrographic type meteorites is the sulfur-containing thiophenes. The presence of this compound class in organic-rich meteorites which have experienced substantial levels of aqueous alteration is relatively unexplored. Early reports of these compounds attributed them to artifacts brought about by reactions between elemental sulfur and organic matter during high temperature extraction and analysis steps. Subsequent investigations confirmed their indigeneity, yet their environment of formation remained unconstrained. Here we present data which suggests that thiophenes are parent body alteration products that reflect the role of liquid water on asteroids in the early solar system.

Sephton, Mark A.↗
DOE OSTI2022

Sulfur-enhanced dynamics of coinage metal(111) surfaces: Step edges versus terraces as locations for metal-sulfur complex formation

The propensity of trace amounts of sulfur adsorbed on coinage metal(111) surfaces to dramatically enhance surface dynamics has been demonstrated by STM observations of accelerated 2D island decay for Cu and Ag. It is generally accepted that this enhancement is due to the formation of adsorbed metal-sulfur complexes, which facilitate surface mass transport of the metal. These complexes were originally proposed to form on terraces following the extraction of metal atoms from step edges and subsequent combination with sulfur on the terraces. However, even when thermodynamically feasible, this mechanism may not be kinetically viable for some complexes due to limited coupling of the complex concentration to the surface diffusion flux of metal atoms. Focusing on the case of Cu, we assess various scenarios where complexes are formed either on terraces or instead directly at step edges, the latter being a new paradigm. In this work, a new pathway is proposed for the formation on terraces. A rich variety of structures incorporating S at step edges exist, which could provide a viable source for complexes, at least from a thermodynamic perspective. However, it is necessary to also assess the activation barrier for complex formation and detachment from step edges. This is facilitated by the nudged-elastic-band analysis of the minimum energy path for this process utilizing machine-learning derived potentials based on density functional theory energetics for the metal-sulfur system.

36 MATERIALS SCIENCE↗
NASA NTRS1999

Engine Test and Measurements

Although the importance of aerosols and their precursors are now well recognized, the characterization of current subsonic engines for these emissions is far from complete. Furthermore, since the relationship of engine operating parameters to aerosol emissions is not known, extrapolation to untested and unbuilt engines necessarily remains highly uncertain. 1997 NASA LaRC engine test, as well as the parallel 1997 NASA LaRC flight measurement, attempts to address both issues by expanding measurements of aerosols and aerosol precursors with fuels containing different levels of fuel sulfur content. The specific objective of the 1997 engine test is to obtain a database of sulfur oxides emissions as well as the non-volatile particulate emission properties as a function of fuel sulfur and engine operating conditions. Four diagnostic systems, extractive and non-intrusive (optical), will be assembled for the gaseous and particulate emissions characterization measurements study. NASA is responsible for the extractive gaseous emissions measurement system which contains an array of analyzers dedicated to examining the concentrations of specific gases (NO, NO(x), CO, CO2, O2, THC, SO2) and the smoke number. University of Missouri-Rolla uses the Mobile Aerosol Sampling System to measure aerosol/particulate total concentration, size distribution, volatility and hydration property. Air Force Research Laboratory uses the Chemical Ionization Mass Spectrometer to measure SO2, SO3/H2SO4, and HN03 Aerodyne Research, Inc. uses Infrared Tunable Diode Laser system to measure SO2, SO3, NO, H2O, and CO2.

Wey, Chown Chou↗
NASA NTRSDate not supplied

Soluble Organic Matter (SOM) analysis of the Hayabusa2 samples: The first results

The Hayabusa2 spacecraft successfully collected the surface and possible sub-surface materials of the asteroid 162173 Ryugu. Ryugu is a C-type asteroid characterized by a low-albedo surface probably consisting of hydrous minerals and carbonaceous materials. [1] The direct optical and spectral analysis of the returned samples indicates that Ryugu material is dominated by hydrous carbonaceous chondrite-like matter (similar to CI chondrites) [2]. Since carbonaceous chondrites have generally yielded various types of organic matter, the collected Ryugu grains are expected to contain diverse types of organic compounds including bio-related molecules. The occurrence of organic compounds in the Ryugu surface will provide clues to the evolution of prebiotic molecules and their preservations associated with aqueous alteration of the primitive asteroid. The initial analysis of soluble organic matter (SOM) of the Hayabusa2-returned samples has been performed by an international team consisting of 32 members. Because the sample amount available for comprehensive SOM analyses is limited, and because the SOM is expected to be present as a complex mixture of various types of organic compounds with very small concentrations of each compound, high-sensitivity and high-resolution analytical techniques have been developed using carbonaceous meteorites [e.g. 3]. Two aggregate samples of the Ryugu grains (A106 and C107) were allocated for the solvent extractions and bulk carbon (C), hydrogen (H), nitrogen (N), sulfur (S) and oxygen (O) measurements. The A106 sample was collected during the 1st sampling in February 2019 and the C107 sample was collected during the 2nd sampling in July 2019 after the Small Carry Impactor (SCI) operation. They consist mainly of particles smaller than 1 mm in diameter, and each sample mass was 38-39 mg. They were firstly investigated spectroscopically in the near infrared wavelength range by the Stone Team prior to the solvent extractions. Other small grains (A0080 and C0057) were also allocated for this study to investigate the spatial distribution of organic compounds on the sample surface. The extraction and analytical measurements implemented by the SOM Team are summarized in Figure 1. Each powder sample was extracted sequentially with non-polar to polar solvents, i.e., hexane, dichloromethane (DCM), methanol (MeOH) and H2O, for non-targeted analysis to reveal the compound composition. Each solvent extract was analyzed by solution state nuclear magnetic resonance (NMR) spectroscopy [4], Fourier transform- ion cyclotron resonance/mass spectrometry (FT-ICR/MS) with ESI and APPI ionization [5] and by high-resolution mass spectroscopy using Orbitrap MS coupled with nano-liquid chromatography (nanoLC/Orbitrap MS) [6], and using two dimensional gas chromatography/mass spectrometry (GC×GC/MS). The extracted residues were passed to the Chemistry Team for further inorganic element analysis. The other powder sample was subjected to the hot water extraction for amino acid analyses including chiral isomer separation, which was performed by three-dimensional (3D) high-performance liquid chromatography (HPLC) with high-sensitivity fluorescence detection (FD) [7] and by HPLC/FD coupled with quadrupole-time of flight/mass spectrometry (QToF/MS) [8]. After the hot water extraction, the residue was split into two halves. One half was further extracted with hydrochloric acid (HCl) to analyze for amino acids in bound-form. The other half was sequentially extracted with DCM/MeOH (1/1) to analyze semi-polar compounds such as polycyclic aromatic hydrocarbons (PAHs) by GC/MS, followed by further extraction with formic acid to analyze polar heterocyclic compounds, and subsequent extraction with HCl to detect bound-form polar compounds. The extracted residues were passed to the IOM Team for the analysis of insoluble organic matter (IOM). Compound-specific stable isotope analyses will be performed using GC/combustion/isotope ratio mass spectrometry (GC/C/IRMS) if the compound concentration is high enough to enable such an isotopic measurement. All extraction procedures were performed on an ISO 6 (Class 100) clean bench inside an ISO 5 (Class 1000) clean room. Baked serpentine powder was also analyzed as a procedural blank. In situ organic compound analysis with the molecular imaging was performed using desorption electrospray ionization (DESI) equipped with Orbitrap MS [9, 10], followed by spatial imaging of organic compounds using ToF/secondary ion mass spectrometry (ToF/SIMS) [11]. The bulk chemical and isotopic compositions of CNS and HO were determined using nano-elemental analysis/isotope ratio mass spectrometry (nanoEA/IRMS) [12] and EA/pyrolysis/IRMS, respectively. We have identified a variety of indigenous organic compounds in the extracts of both A106 and C107 samples. The Ryugu grains host organic molecules under the high-vacuum and cosmic-ray irradiation environment of the asteroid surface. The analysis of extracted molecules is in progress, and the first results will be presented at the symposium.

Hiroshi Naraoka↗
DOE OSTI2024

Recovery of Rare Earths, Precious Metals and other Critical Materials from Geothermal Waters with Advanced Sorbent Structures - CRADA 355 (Abstract)

The ability to recover valuable trace level minerals from geothermal brines using high-performance solid-phase sorbents will be explored and developed. A compressive range of sorbent materials will be screened for application to metal extraction from geothermal brines. Preferred sorbents from extraction of trace levels of rare earths (REs), precious metals (PMs), and other critical/strategically valuable materials (CMs) such as Zn, Mn, Te, Sc, Se and U from geothermal brines will be identified. For the preferred sorbents PNNL will determine the volumes they are capable of providing efficient extraction from. The thermal and chemical limits (including, acid, sulfur, salt) for performance of the preferred sorbent materials will be determined; with a target of at least 125°C and perhaps as high as 400° C. Sorbent form factors (including, packed bed, membrane, mats) that can function efficiently and be installed cost effectively in geothermal energy plants will be assessed for chemical and economic viability. Material regeneration and cyclic utilization will be demonstrated, targeting hundreds to thousands of cycles. Options for recovery and purification (including, selective separation of heavy REs) of collected materials will be explored. A techno-economic analysis (TEA) will be performed to assess the best approach to provide a value-added extraction process for geothermal energy systems. The sorbent materials and engineering analysis will be applicable to other industrial processes in which secondary recovery of valuable materials could provide economic benefit.

15 GEOTHERMAL ENERGY↗
DOE OSTI2020

A new Devonian euthycarcinoid reveals the use of different respiratory strategies during the marine-to-terrestrial transition in the myriapod lineage

Myriapods were, together with arachnids, the earliest animals to occupy terrestrial ecosystems, by at least the Silurian. The origin of myriapods and their land colonization have long remained puzzling until euthycarcinoids, an extinct group of aquatic arthropods considered amphibious, were shown to be stem-group myriapods, extending the lineage to the Cambrian and evidencing a marine-to-terrestrial transition. Although possible respiratory structures comparable to the air-breathing tracheal system of myriapods are visible in several euthycarcinoids, little is known about the mechanism by which they respired. Here, we describe a new euthycarcinoid from Upper Devonian alluvio-lagoonal deposits of Belgium. Synchrotron-based elemental X-ray analyses were used to extract all available information from the only known specimen. Sulfur X-ray fluorescence (XRF) mapping and spectroscopy unveil sulfate evaporation stains, spread over the entire slab, suggestive of a very shallow-water to the terrestrial environment prior to burial consistent with an amphibious lifestyle. Trace metal XRF mapping reveals a pair of ventral spherical cavities or chambers on the second post-abdominal segment that do not compare to any known feature in aquatic arthropods, but might well play a part in air-breathing. Our data provide additional support for amphibious lifestyle in euthycarcinoids and show that different respiratory strategies were used during the marine-to-terrestrial transition in the myriapod lineage.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS2003

Thermococcus Thioreducens sp. nov., A Novel Hyperthermophilic, Obligately Sulfur-Reducing Archaeon from a Deep-Sea Hydrothermal Vent

A novel hyperthermophilic organo-heterotrophic archaeon, strain OGL-20P(sup T), was isolated from 'black smoker' chimney material from the Rainbow hydrothermal vent site on the Mid-Atlantic Ridge (36.2 N; 33.9 W). The cells of strain OGL-20P(sup T) have an irregular coccoid shape and are motile with a single flagellum. Growth was observed to occur within the pH range 5.0-8.5 (optimum pH 7.0), NaCl concentration range 1-5 % (w/v) (optimum 3 %), and temperature range 55-94 C (optimum 83-85 C). Novel isolate is strictly anaerobic and obligately dependent from elemental sulfur as electron acceptor, but it cannot reduce sulfate, sulfite, thiosulfate, iron (III) or nitrate. Proteolysis products that can be utilized as substrates during sulfur-reduction are: peptone, bactotryptone, casamino-acids, and yeast extract. Strain OGL-20P(sup T) is resistant to ampicillin, chloramphenicol, kanamycin, and gentamycin, but sensitive to tetracycline and rifampicin. The G+C content of DNA is 57.1 mol% . Comparative 16S rRNA gene sequence analysis revealed that strain OGL-20P(sup T) is most closely related to Thermococcus celer and 'T. barossii', but no significant homology by DNA-DNA hybridization was observed between those species and the new isolate. On the basis of physiological and molecular properties of the new isolate, the name Thermococcus thioreducens sp. nov., is proposed. The type strain is OGL-20P(sup T) (= ATCC BAA-394(sup T) = DSM 1498(sup T)).

Pikuta, Elena V.↗
NASA NTRS2010

Prebiotic Synthesis of Methionine and Other Sulfur-Containing Organic Compounds on the Primitive Earth: A Contemporary Reassessment Based on an Unpublished 1958 Stanley Miller Experiment

Original extracts from an unpublished 1958 experiment conducted by the late Stanley L. Miller were recently found and analyzed using modern state-of-the-art analytical methods. The extracts were produced by the action of an electric discharge on a mixture of methane (CH4), hydrogen sulfide (H2S), ammonia (NH3), and carbon dioxide (CO2). Racemic methionine was farmed in significant yields, together with other sulfur-bearing organic compounds. The formation of methionine and other compounds from a model prebiotic atmosphere that contained H2S suggests that this type of synthesis is robust under reducing conditions, which may have existed either in the global primitive atmosphere or in localized volcanic environments on the early Earth. The presence of a wide array of sulfur-containing organic compounds produced by the decomposition of methionine and cysteine indicates that in addition to abiotic synthetic processes, degradation of organic compounds on the primordial Earth could have been important in diversifying the inventory of molecules of biochemical significance not readily formed from other abiotic reactions, or derived from extraterrestrial delivery.

Parker, Eric T.↗
DOE OSTI2026

Extraction of lithium from battery recycling wastewater using synergistic D2EHPA and TBP

The recycling of spent lithium-ion batteries (LIBs) poses significant challenges, including the generation of large volumes of chemically complex wastewater. The composition of this wastewater is influenced by both the intrinsic chemistry of the batteries and the specific recycling processes employed. Notably, this wastewater contains economically valuable components, such as lithium, which can be recovered. Here, in this study, a solvent extraction (SX) process was investigated as a method to recover lithium from battery recycling wastewater, especially from anode-washing stage. Initially, various commercial extractants were evaluated, including di(2-ethylhexyl)phosphoric acid (D2EHPA), mono-2-ethylhexyl (2-ethylhexyl)phosphonate (PC88A), bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex 272), 2-hydroxy-5-nonylacetophenone oxime (LIX 84-I), tri-butyl phosphate (TBP), and their combinations. Among these, D2EHPA + TBP demonstrated a synergism to advance and maximize the lithium extraction. Subsequently, the effects of key parameters, including D2EHPA concentration, TBP concentration, contact time, initial pH, and aqueous-to-organic (A/O) phase ratio, were systematically investigated and optimized. A two-stage SX approach was employed to enhance lithium recovery. Under the optimized conditions of 30.0 vol% D2EHPA, 10.0 vol% TBP, 10 min of contact time, and a 1:1 A/O phase ratio, a lithium extraction efficiency of more than 88% in a two-stage solvent extraction was achieved. Lithium was subsequently stripped from the loaded organic solution using sulfuric acid (H 2 SO 4 ). Using 2.0 M H 2 SO 4 , lithium stripping was achieved after two counter-current stripping stages at an organic-to-aqueous (O/A) phase ratio of 6:1. This stripping process enriched the lithium concentration by a factor of four compared to the original lithium concentration in the anode-washing wastewater. The recyclability of the synergistic D2EHPA + TBP system was also evaluated over four extraction-stripping cycles. The results demonstrated that the system maintained high extraction and stripping efficiencies.

D2EHPA↗
DOE OSTI2021

Lipophilic diglycolamide compounds for extraction of rare earth metals from aqueous solutions

A method for extracting rare earth metals (e.g., lanthanides and/or actinides) from aqueous solution, the method comprising: (i) acidifying an aqueous solution containing said rare earth metals with sulfuric acid to result in an acidified aqueous solution containing 1-12 M concentration of sulfuric acid; and (ii) contacting the acidified aqueous solution with an aqueous-insoluble hydrophobic solution comprising a rare earth extractant molecule dissolved in an aqueous-insoluble hydrophobic solvent to result in extraction of one or more of the rare earth metals into the aqueous hydrophobic solution, wherein the rare earth extractant molecule has the following structure: wherein R1, R2, R3, and R4 are independently selected from hydrocarbon groups containing 1-20 carbon atoms, provided that the total carbon atoms in R1, R2, R3, and R4 is at least 12; and R5 and R6 are independently selected from hydrogen atom and hydrocarbon groups containing 1-3 carbon atoms.

Brigham, Derek↗