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NASA NTRSDate not supplied

Ramdb: The NASA Raman Spectral Database (version 1.00).

Given that, in most instances, minimal sample preparation is required and due to its contactless instrument design, Raman spectroscopy is one of the most versatile vibrational spectroscopic techniques for the chemical analysis of environmental and biological specimens. The diversity of applications of Raman spectroscopy ranges anywhere from art [1] to planetary science missions [2]. The advancement in the use of Raman spectroscopy in Solar System missions, notably in post-mission sample return analysis, requires a spectral library holding the broad range of specimens that could be found in Solar System sources. For this purpose, we have initiated the development of a Raman spectral database (Ramdb) at NASA Ames Research Center. Currently, the database includes experimental and theoretical Raman spectra of PAHs [3, 4], as well as laboratory Raman spectra of amino acids, carbon allotropes, minerals, and analogs relevance to Earth Sciences [5], Exobiology [6], Planetary [7], and Astrochemistry [8] to name just a few examples. Ramdb can be found on the web at www.astrochemistry.org/ramdb, where raw and processed Raman spectra can be downloaded in CSV format. The laboratory Raman spectra are measured using a laser Raman spectrometer (JASCO NRS-5500-532QRI). The Raman instrument is equipped with three excitation lasers, with wavelengths of 405, 532, and 785 nm. A clean silicon substrate is used as the internal standard for wavenumber calibration. Powdered samples were prepared (microscopic >10 um, grounded microscopic < 10 um) on glass slides. Some raw data exhibited a background signal arising as a combination of laser-induced fluorescence from the sample. To correct this background, we developed a Python pipeline that uses open-source Python libraries. Ramdb provides both raw and processed (using Python pipeline) data, which includes tabulated Raman shift transitions and other measurement details. The theoretical Raman band positions of PAHs (pyrene monomers and tetramer clusters) were computed using density functional theory (DFT) with the help of the Gaussian 16 suite of programs [9]. In the near future, Ramdb will serve as a repository of Raman spectral data from Laboratory Astrophysics and Planetary Science experiments involving the irradiation of organic compounds under simulated space and planetary conditions. In addition, online and offline tools will be developed for utilising the database for comparison to the user’s sample.

N Punnakayathil↗
DOE OSTI2024

Direct observation of twisted stacking domains in the van der Waals magnet CrI 3

Van der Waals (vdW) stacking is a powerful technique to achieve desired properties in condensed matter systems through layer-by-layer crystal engineering. A remarkable example is the control over the twist angle between artificially-stacked vdW crystals, enabling the realization of unconventional phenomena in moiré structures ranging from superconductivity to strongly correlated magnetism. Here, we report the appearance of unusual 120° twisted faults in vdW magnet CrI 3 crystals. In exfoliated samples, we observe vertical twisted domains with a thickness below 10 nm. The size and distribution of twisted domains strongly depend on the sample preparation methods, with as-synthesized unexfoliated samples showing tenfold thicker domains than exfoliated samples. Cooling induces changes in the relative populations among different twisting domains, rather than the previously assumed structural phase transition to the rhombohedral stacking. The stacking disorder induced by sample fabrication processes may explain the unresolved thickness-dependent magnetic coupling observed in CrI 3 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Characterization of Tank 15H Sample in Support of Preliminary Cease Waste Removal and Closure Mode Determination

The Savannah River National Laboratory (SRNL) was requested by Savannah River Mission Completion (SRMC) to provide sample preparation and analysis of Tank 15H characterization samples. These samples follow an interest in exploring avenues to condense the extensive sampling of the Tank Closure process. One such pathway would be to collect a sample during an earlier waste removal campaign for analysis to determine comparability to the later residual tank inventory determined through Residual Material sampling and characterization prior to grouting. Six Tank 15H samples (HTF-15-24-9, HTF- HTF-15-24-10, HTF-15-24-11, HTF-15-24-12, HTF&#x2;15-24-13, and HTF-15-24-14) were delivered to SRNL in May of 2024. These six Tank 15H samples were taken as close as possible to the solids layer of the Tank 15H. These six Tank 15H samples were combined to form one composite sample for characterization due to the lack of sufficient solids fraction.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NASA NTRS1995

Aqueous nitrite ion determination by selective reduction and gas phase nitric oxide chemiluminescence

An improved method of flow injection analysis for aqueous nitrite ion exploits the sensitivity and selectivity of the nitric oxide (NO) chemilluminescence detector. Trace analysis of nitrite ion in a small sample (5-160 microL) is accomplished by conversion of nitrite ion to NO by aqueous iodide in acid. The resulting NO is transported to the gas phase through a semipermeable membrane and subsequently detected by monitoring the photoemission of the reaction between NO and ozone (O3). Chemiluminescence detection is selective for measurement of NO, and, since the detection occurs in the gas-phase, neither sample coloration nor turbidity interfere. The detection limit for a 100-microL sample is 0.04 ppb of nitrite ion. The precision at the 10 ppb level is 2% relative standard deviation, and 60-180 samples can be analyzed per hour. Samples of human saliva and food extracts were analyzed; the results from a standard colorimetric measurement are compared with those from the new chemiluminescence method in order to further validate the latter method. A high degree of selectivity is obtained due to the three discriminating steps in the process: (1) the nitrite ion to NO conversion conditions are virtually specific for nitrite ion, (2) only volatile products of the conversion will be swept to the gas phase (avoiding turbidity or color in spectrophotometric methods), and (3) the NO chemiluminescence detector selectively detects the emission from the NO + O3 reaction. The method is free of interferences, offers detection limits of low parts per billion of nitrite ion, and allows the analysis of up to 180 microL-sized samples per hour, with little sample preparation and no chromatographic separation. Much smaller samples can be analyzed by this method than in previously reported batch analysis methods, which typically require 5 mL or more of sample and often need chromatographic separations as well.

NASA Discipline Environmental Health↗
NASA NTRS2009

NM-Scale Anatomy of an Entire Stardust Carrot Track

Comet Wild-2 samples collected by NASA s Stardust mission are extremely complex, heterogeneous, and have experienced wide ranges of alteration during the capture process. There are two major types of track morphologies: "carrot" and "bulbous," that reflect different structural/compositional properties of the impactors. Carrot type tracks are typically produced by compact or single mineral grains which survive essentially intact as a single large terminal particle. Bulbous tracks are likely produced by fine-grained or organic-rich impactors [1]. Owing to their challenging nature and especially high value of Stardust samples, we have invested considerable effort in developing both sample preparation and analytical techniques tailored for Stardust sample analyses. Our report focuses on our systematic disassembly and coordinated analysis of Stardust carrot track #112 from the mm to nm-scale.

Nakamura-Messenger, K.↗
NASA NTRS2024

Plasma-Based Elemental Analyzer for Crewed Transit and Planetary Habitation

As NASA continues to perform research on the ISS and move towards the Moon and Mars, it is important for astronauts to have a technology capable of determining the composition of solid, liquid, and gas samples. Currently, samples are transported back to Earth for analysis, which may impact results due to the time delay of samples waiting to be returned to Earth as well as potential sample contamination from re-entry, change in environment, and various personnel handling. Therefore, researchers at the Applied Chemistry Lab at KSC have developed a proof-of-concept “Plasma-Based Elemental Analyzer,” which has the capability of testing solid, liquid, and gas samples for identification. Currently, the analysis is only qualitative, with quantitative identification left for future work. This technology is similar to ICP-OES, but differs in instrument size and sample preparation. Both technologies use plasma to ionize samples for light emission. The plasma elemental analyzer aims to be portable and lightweight, require only electrical power, and analyze solid, liquid, and gas samples. It does not use acid digestion or a nebulizer, requires less power than ICP-OES, and is able to operate with minimal to no usage of argon gas. Furthermore, the plasma elemental analyzer operates within low power constraints, which makes it feasible for usage on future missions with higher power constraints. The technology was tested at atmospheric pressure using mostly room air as the carrier gas for plasma production in the proof-of-concept study. The results showed the peak signals of the elements with an associated arbitrary signal intensity that allowed for qualitative identification. Solid samples that were tested included inedible biomass from the Golden Heirloom Cherry Tomato plant and Lunar Highlands Simulants (LHS-1). The liquid samples included elements of interest for the space crop production community. This work showed that a system smaller than the traditional ICP-OES equipment is able to be designed and implemented in future use cases, although it requires further development.

Kenneth Engeling↗
NASA NTRSDate not supplied

Center for Isotope Cosmochemistry and Geochronology at NASA Johnson Space Center

Ten years in the making the Center for Isotope Cosmochemistry and Geochronology (CICG) at NASA Johnson Space Center is designed to be a cooperative analytical facility where novel techniques are developed and performed. Our team works collaboratively to operate this integrated lab suite comprising sample preparation, metal-free clean chemistry, and mass spectrometers to measure a wide variety of elements and isotopes in astromaterials. Contamination control is enacted throughout by a positive pressure cascade of HEPA filtered air, weekly surface cleaning and particle counting. Astromaterials processing is performed with application-specific mortar and pestles, heavy liquid separation, a Frantz magnetic separator, as well as hand-picking using optical microscopes in laminar flow boxes. Microsampling is also carried out using a New Wave MicroMill. Elements for isotopic analysis are isolated from acid-digested samples using ion-exchange chromatography. Cross-contamination is minimized with dedicated laminar flow boxes and labware for different purification protocols. Instrumentation includes a ThermoFisher Element XR inductively coupled plasma mass spectrometer (ICP-MS) for quantification of elemental concentrations in dissolved sample solutions. For in situ analysis, a Teledyne Photon Machines Analyte Excite+ laser ablation system is coupled to the Element XR. The ThermoFisher Triton thermal ionization mass spectrometer (TIMS) is used to measure the isotopic composition of elements such as CA, K, Cr, Rb, Sr, Sm, Nd at high precision in processed samples. For a more diverse range of isotopic analyses, CICG houses a Nu Sapphire 1700 multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS), which is a large geometry instrument with a multi-pole collision cell for interference removal. An Applied Spectra Instruments J200 femto-second laser is planned for install this Fall and will be coupled to the Nu Sapphire 1700. NASA’s Internal Scientist Funding Model (ISFM)supports this facility. Advanced analytical geochemistry techniques are applied to targeted astromaterials to address important problems in planetary sciences, with a longer-term goal of preparing for samples collected and returned by space missions. CICG is open to collaborations on projects that utilize the facility’s unique capabilities and are within its research scope. We are particularly eager to support and share expertise with the next generation of planetary scientists.

Justin I Simon↗
NASA NTRSDate not supplied

Effect of Vacuum on Force Response of an Ultrasonic Penetrator

Introduction: The Apollo astronauts encountered higher than expected resistances when interacting with the lunar soil via the Apollo Lunar Surface Drill (ALSD) and the trenching tool. Reducing the force required to move tools or other mechanical components through regolith will impact many steps of the resource extraction process. Force reduction has been achieved in soil materials by imparting vibration to tooling interfaces such as a vibratory farming cultivator, a percussive scoop, and ultrasonically resonant penetrators. Vibration-assisted tools in granular media reduce interaction forces by fluidizing a volume around the tool, allowing the tool to progress through a dynamic (fluid) medium instead of a static (solid) medium. This work seeks to quantify ultrasonic vibration’s effect on the force response of a penetrator in lunar soil simulant in vacuum sufficient to be within the molecular flow regime of any disturbed gases. Methods: A custom vacuum chamber setup, CUBEvac, was designed and built to facilitate penetration testing in a high vacuum environment, for comparison to penetration behavior in ambient terrestrial environment. A two-stage pumping system (Agilent Triscroll 600 roughing pump, Agilent VHS-6 oil diffusion pump) reached chamber pressures of about 5x10-6 Torr with regolith simulant in place. Figure 1 is a schematic of the heart of the assembly (note the penetration drive mechanisms above the chamber feedthrough and the regolith simulant sample in the bottom are not shown). The penetration actuation stack was comprised of a stepper motor driving a lead screw to move the ultra-sonic probe vertically inside the chamber. Motion was coordinated with an Arduino Uno. GRC-3 lunar simulant was used for this set of experiments. Samples were prepared in a four-liter stain-less steel, cylindrical pot with an internal diameter of approximately 15.56 cm (6.125 in) and a depth of 19.37 cm (7 5/8 in) for testing. The soil was baked out prior to compaction preparation as a measure to reduce soil moisture which interfered with pump down capacity. The soil was not baked again if it was removed from the vacuum chamber, prepped, and immediately returned to the vacuum chamber for pump down. The soil was compacted using a 60 Hz vibration table with a surcharge of 34 kg place on top of the soil in the container. Prepared soil samples weighed approximately 6.5 kg (bulk density 1.895-1.934 g/cm3). Two probe end effectors were tested: A cone penetrometer (static only) with a nominal diameter of 12.7 mm (0.5 in) and a nominal height of 28.6 mm (1.125 in); and a vibrating cylindrical probe measuring 12.7 mm in diameter and 50.8 mm in effective length from the tip (Figure 2). The cylindrical probe vibrated resonantly at 20 kHz with an amplitude 23 μm. The cone penetration tests were conducted to assess potential soil behavior differences in vacuum. The cylinder probe tests were conducted as the primary subject of this investigation to assess force response in vacuum. For each test, a regolith simulant sample was load-ed and compacted in the chamber, which was then evacuated for roughly 18 hours to reach the lowest possible pressure (approximately 5x10-6 Torr for most tests). The probe was then moved to about 10 mm above the soil surface before being pushed to a depth of 50 mm for the cylinder probe tests and to a depth of 100 mm for the cone penetrometer tests, both at a speed of 2 mm/s. The simulant samples were prepared the same for all tests. Ideally, they would respond consistently to probe penetration under ambient and vacuum conditions. This was evaluated by measuring the resistance of representative prepared simulant beds with a standard cone penetrometer in both environments. Results and Discussion: The resistance of the simulant samples in the vacuum tests was consistently lower than in the ambient tests as determined by the cone penetration tests. Thus, the ambient and vacuum results cannot be compared directly; work is underway to de-confound and better correlate the data. Still, figures 3-6 show that probe penetration forces are lower overall in the vacuum environment. In both environments, resonant vibration of the probe provides two useful effects: It reduces the probe penetration force and smooths the force-depth curve, significantly reducing local maxima. These effects have implications for various potential applications, such as astronaut hand-tools, where benefits (reducing astronaut effort) outweigh the cost of the additional energy re-quired to generate vibration. These results demonstrate that resonantly vibrating tools can meaningfully reduce the penetration force required for excavation, probing, and drilling tools in simulated lunar regolith deposits under vacuum levels approaching those that will be experience on the Moon’s surface. Lunar-gravity, ambient environment tests are scheduled soon. The effects of realistic temperatures and temperature gradients and deeper vacuum remain to be tested.

E Rezich↗
DOE OSTI2025

Microstructural evaluation of thin-wall sections of 316L stainless steel produced by laser powder-bed fusion processing

The synthesis of thin wall sections that are only 0.4 mm thick is achieved with LPBF AM. Sample preparation is optimized using metallographic polishing to produce samples with only 0.3 um rms roughness for scanning electron microanalysis with EBSD and EDS. A fully austenitic 316L phase is found without evidence of secondary phases. Unlike some AM products that can readily evidence composition segregation due to solute rejection as attributable to temperature gradients within the solidification

Jankowski, Alan F. [Sandia National Laboratories (↗
NASA NTRS2010

Automated Desalting Apparatus

Because salt and metals can mask the signature of a variety of organic molecules (like amino acids) in any given sample, an automated system to purify complex field samples has been created for the analytical techniques of electrospray ionization/ mass spectroscopy (ESI/MS), capillary electrophoresis (CE), and biological assays where unique identification requires at least some processing of complex samples. This development allows for automated sample preparation in the laboratory and analysis of complex samples in the field with multiple types of analytical instruments. Rather than using tedious, exacting protocols for desalting samples by hand, this innovation, called the Automated Sample Processing System (ASPS), takes analytes that have been extracted through high-temperature solvent extraction and introduces them into the desalting column. After 20 minutes, the eluent is produced. This clear liquid can then be directly analyzed by the techniques listed above. The current apparatus including the computer and power supplies is sturdy, has an approximate mass of 10 kg, and a volume of about 20 20 20 cm, and is undergoing further miniaturization. This system currently targets amino acids. For these molecules, a slurry of 1 g cation exchange resin in deionized water is packed into a column of the apparatus. Initial generation of the resin is done by flowing sequentially 2.3 bed volumes of 2N NaOH and 2N HCl (1 mL each) to rinse the resin, followed by .5 mL of deionized water. This makes the pH of the resin near neutral, and eliminates cross sample contamination. Afterward, 2.3 mL of extracted sample is then loaded into the column onto the top of the resin bed. Because the column is packed tightly, the sample can be applied without disturbing the resin bed. This is a vital step needed to ensure that the analytes adhere to the resin. After the sample is drained, oxalic acid (1 mL, pH 1.6-1.8, adjusted with NH4OH) is pumped into the column. Oxalic acid works as a chelating reagent to bring out metal ions, such as calcium and iron, which would otherwise interfere with amino acid analysis. After oxalic acid, 1 mL 0.01 N HCl and 1 mL deionized water is used to sequentially rinse the resin. Finally, the amino acids attached to the resin, and the analytes are eluted using 2.5 M NH4OH (1 mL), and the NH4OH eluent is collected in a vial for analysis.

Spencer, Maegan K.↗
NASA NTRS2011

The Laser Ablation Ion Funnel: Sampling for in situ Mass Spectrometry on Mars

A considerable investment has been made by NASA and other space agencies to develop instrumentation suitable for in situ analytical investigation of extra terrestrial bodies including various mass spectrometers (time-of-flight, quadrupole ion trap, quadrupole mass filters, etc.). However, the front-end sample handling that is needed to collect and prepare samples for interrogation by such instrumentation remains underdeveloped. Here we describe a novel approach tailored to the exploration of Mars where ions are created in the ambient atmosphere via laser ablation and then efficiently transported into a mass spectrometer for in situ analysis using an electrodynamic ion funnel. This concept would enable elemental and isotopic analysis of geological samples with the analysis of desorbed organic material a possibility as well. Such an instrument would be suitable for inclusion on all potential missions currently being considered such as the Mid-Range Rover, the Astrobiology Field Laboratory, and Mars Sample Return (i.e., as a sample pre-selection triage instrument), among others.

Johnson, Paul V.↗
NASA NTRS2011

An Examination of the Space Weathering Patina of Lunar Rock 76015

Space weathering discussions have generally centered around soils but exposed rocks will also incur the effects of weathering. Rocks have much longer surface lifetimes than an individual soil grain and thus record a longer history of exposure. By studying the weathering products which have built up on a rock surface, we can gain a deeper perspective on the weathering process and better assess the relative importance of various weathering components. The weathered coating, or patina, of the lunar rock 76015 has been previously studied under SEM and also by TEM using ultramicrotome sample preparation methods. However, to really understand the products involved in creating these coatings, it is helpful to examine the patina in cross section, something which is now possible though the use of Focused Ion Beam (FIB) sample prep techniques, which allows us to preserve intact the delicate stratigraphy of the patina coating and provides a unique cross-sectional view of the space weathering process. Several samples have been prepared from the rock and the coatings are found to be quite variable in thickness and composition from one sample to the next.

Noble, S.↗
NASA NTRS2014

A Novel Hybrid Ultramicrotomy/FIB-SEM Technique: Preparation of Serial Electron-Transparent Thin Sections of a Hayabusa Grain

The Japanese space agency's (JAXA) Hayabusa mission returned the first particulate samples (typically <100micron) from the surface of an asteroid (25143 Itokawa). These precious samples provide important insights into early Solar System processes, but their sizes pose tremendous challenges to coordinated analysis using a variety of nano- and micro-beam techniques. The ability to glean maximal information from individual particles has become increasingly important and depends critically on sample preparation. We developed a hybrid technique combining traditional ultramicrotomy with focused ion beam (FIB) techniques, allowing for more thorough in situ investigations of grain surfaces and interiors. Using this method, we increase the number of FIB-prepared sections that can be recovered from a particle with dimensions on the order of tens of microns. These sections can be subsequently analyzed using a variety of analytical techniques. Particle RA-QD02-0211 is a approx. 40×40×20 micron particle from Itokawa containing olivine and Fe sulfides. It was embedded in low viscosity epoxy and partly sectioned to a depth of approx 10 micron; sections are placed on Cu grids with thin amorphous films for transmission electron microscope (TEM) analyses. With the sample surface partly exposed, the epoxy bullet is trimmed to a height of approx. 5mm to accommodate the allowable dimensions for FIB work (FEI Quanta 600 3D dual beam FIB-SEM). Using a diamond trim knife, the epoxy surrounding the grain is removed on 3 sides (to within a few microns of the grain); the depth of material removed extends well below the bottom of the particle. The sample is attached to an SEM pin mount, the epoxy coated with conductive paint, and the entire assembly coated with approx. 40nm of carbon to eliminate sample charging during FIB work. A protective carbon cap is placed according to the plan for the 15 FIB sections. The central 'spine' of the cap runs perpendicular to the front of the sample, and the 'ribs' protruding from either side run parallel. Each rib indicates the location of a planned FIB section, and the spine contains the final two planned sections. We use a cap with a 4 micron-wide spine and 2micron-wide ribs that have ≳3.5 micron of space between them (narrower cuts result in too much re-deposition of material inside the trenches). Using a 30kV, 3nA ion-beam we expose the front surface of the grain and commence milling trenches between sections. Rather than using the typical C-cut to prepare the sample for lift-out, an L-cut is used instead, leaving the sample connected by an interior tab. tab. Sections are lifted out, attached to TEM grids and thinned to electron transparency. TEM analyses show that our hybrid technique preserves both interior and edge features, including surface modifications from exposure to the space environment, such as damaged rims that form in response to solar wind implantation effects and adhering grains. In addition, the FIB sections provide larger areas that are free of fractures and chatter effects in comparison to the microtome thin sections, thus enabling more accurate measurements of solar flare particle track densities that are used to determine the surface exposure age of the particles.

Berger, Eve L.↗
NASA NTRS2017

Advanced Curation Activities at NASA: Preparation for Upcoming Missions

The responsibility for curating NASA's astromaterials collections falls to the NASA Curation Office at Johnson Space Center. Under the governing document, NASA Policy Directive (NPD) 7100.10F and derivative requirements documents, JSC is charged with curation of all extraterrestrial material under NASA control, including future NASA missions to include material returned in Mars Sample Return (MSR) efforts, OSIRIS-REx, NASA's subset of Hayabusa-2 samples, and any other sample return missions. The Directive defines Curation as activities including documentation, preservation, sample preparation, distribution, and tracking of samples for research, education, and public outreach. In this abstract we will describe Curation's research and development efforts to improve the care of existing collections and prepare for future NASA sample return missions. These efforts are collectively referred to as Advanced Curation, a term first coined in 2002.

Fries, M. D.↗
NASA NTRS1975

Effects of multifunctional crosslinking agents on the thermomechanical properties of polyimide films

The potential of high temperature resistant polymers such as polyimides (PI) and polyphenylquinoxalines (PPQ) as matrix resins in fiber-reinforced composites has not been fully realized to date. One of the problems associated with these resins is that they exhibit creep, or thermoplastic yielding under load at temperatures approaching 316 C (600 F). The purpose of this investigation was to further reduce thermoplastic behavior of polyimide resins by substituting a controlled amount of the diamine monomer with crosslinking agents having a higher amine functionality. The knowledge gained from a study of the thermomechanical properties of the crosslinked resins would then be used in the fabrication of fiber-reinforced polyimide composites. This report describes the synthesis and characterization of three new polyfunctional amines. Polyimide films containing varying amounts of the cross-linking agents were prepared, and their properties compared with those of control samples prepared with difunctional amines. The effect of crosslink density on isothermal weight loss, polymer softening, and glass transition temperatures is discussed.

Delvigs, P.↗
NASA NTRS1978

Determination of oxygen in silicon and carbide by activation with 27.2 meV alpha particles

The Si sample was polished on one side, and on the other side Ni was applied chemically and soldered with Pb to a water cooled Cu substrate. Optical quartz standard was fixed from the other side. Si carbide samples were soldered to a substrated with In. The prepared samples were irradiated in a cyclotron with a 27.2 MeV alpha particle beam. The layers were removed from the Si and Si carbide samples by grinding and the positron activity of F-18(t sub 1/2 110 min) was measured by using a gamma, gamma coincidence spectrometer with two NaI(TI) crystals. For analysis of Si carbide, the activity decay curve of the samples was recorded to find the contribution of the positron activity of Cu-65(t sub 1/2 12.9 hr) which formed from Ni impurity on irradiation.

Dolgolenko, A. P.↗