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At least 109 records · Page 6

Petrologic evolution of CM chondrites: The difficulty of discriminating between nebular and parent-body effects

We wish to draw attention to a major controversy that has arisen in the area of CM-chondrite petrology. The problem is important because its resolution will have profound implications for ideas concerning nebular dynamics, gas-solid interactions in the nebula, and accretionary processes in the nebula, among other issues. On the one hand, cogent arguments have been presented that 'accretionary dust mantles,' were formed in the solar nebula prior to accretion of the CM parent asteroid(s). On the other hand, no-less-powerful arguments have been advanced that a significant fraction of the CM lithology is secondary, produced by aqueous alteration in the near-surface regions of an asteroid-sized object. Because most, if not all, CM chondrites are breccias, these two views could coexist harmoniously, were it not for the fact that some of the coarse-grained lithologies surrounded by 'accretion dust mantles' are themselves of apparently secondary origin. Such an observation must clearly force a reassessment of one or both of the present schools of thought. Our objective here is to stimulate such a reassessment. Four possible resolutions of this conflict may be postulated. First, perhaps nature found a way of permitting such secondary alteration to take place in the nebula. Second, maybe dust mantles could form in a regolith, rather than a nebular, environment. Third, it is possible that dust mantles around secondary lithologies are different from those around primary lithologies. Finally, perhaps formation of CM chondrites involved a more complex sequence of events than visualized so far, so that some apparently 'primary' processes postdated certain 'secondary' processes.

Kerridge, J. F.↗

Operating Characteristics of a 15-cm dia. Ion Engine for Small Planetary Spacecraft

A 15-cm diameter, scaled-down version of the NASA light-weight 30-cm ion engine has been developed for potential application to very small planetary spacecraft. Integration of the 15-cm ion source into 4x15-cm segmented engine configuration results in a 30-cm equivalent engine which can be throttled over a 7-to-1 input power variation with a constant beam current in each of the four segments. Throttling the segmented engine by turning off individual segments can result in a significant decrease in the required service life (and qualification requirements) of the ion source components.

grids segmented ion engine↗

Oxygen-isotopic Compositions of Low-FeO relicts in High-FeO Host Chondrules in Acfer 094, a Type 3.0 Carbonaceous Chondrite Closely Related to CM

With one exception, the low-FeO relict olivine grains within high-FeO porphyritic chondrules in the type 3.0 Acfer 094 carbonaceous chondrite have DELTA O-17 ( = delta O-17 - 0.52 X delta O-18) values that are substantially more negative than those of the high-FeO olivine host materials. These results are similar to observations made earlier on chondrules in C03.0 chondrites and are consistent with two independent models: (1) Nebular solids evolved from low-FeO, low-DELTA O-17 compositions towards high-FeO, more positive DELTA O-17 compositions; and (2) the range of compositions resulted from the mixing of two independently formed components. The two models predict different trajectories on a DELTA O-17 vs. log Fe/Mg (olivine) diagram, but our sample set has too few values at intermediate Fe/Mg ratios to yield a definitive answer. Published data showing that Acfer 094 has higher volatile contents than CO chondrites suggest a closer link to CM chondrites. This is consistent with the high modal matrix abundance in Acfer 094 (49 vol.%). Acfer 094 may be an unaltered CM chondrite or an exceptionally matrix-rich CO chondrite. Chondrules in Acfer 094 and in CO and CM carbonaceous chondrites appear to sample the same population. Textural differences between Acfer 094 and CM chondrites are largely attributable to the high degree of hydrothermal alteration that the CM chondrites experienced in an asteroidal setting.

Rubin, Alan E.↗

Relationship Between Iron Valence States of Serpentine in CM Chondrites and Their Aqueous Alteration Degrees

The 0.6-0.7 micron absorption band observed for C-type asteroids is caused by the presence of Fe(3+) in phyllosilicates . Because Fe-bearing phyllosilicates, especially serpentine, are the most dominant product of aqueous alteration in the most abundant carbonaceous chondrites, CM chondrites, it is important to understand the crystal chemistry of serpentine in CM chondrites to better understand spectral features of C-type asteroids. CM chondrites show variable degrees of aqueous alteration, which should be related to iron valences in serpentine. It is predicted that the Fe(3+)/Sum of (Fe) ratios of serpentine in CM chondrites decrease as alteration proceeds by Si and Fe(3+) substitutions from end-member cronstedtite to serpentine, which should be apparent in the absorption intensity of the 0.6-0.7 micron band from C-type asteroids. In fact, the JAXA Hayabusa 2 target (C-type asteroid: 1993 JU3) exhibits heterogeneous spectral features (0.7 micron absorption band disappears by rotation). From these points of view, we have analyzed iron valences of matrix serpentine in several CM chondrites which span the entire observed range of aqueous alteration using Synchrotron Radiation X-ray Absorption Near-Edge Structure (SR-XANES). In this abstract we discuss the relationship between obtained Fe(3+)/Sum of (Fe) ratios and alteration degrees by adding new data to our previous studies

Mikouchi, T.↗

What Are Space Exposure Histories Telling Us about CM Carbonaceous Chondrites?

Chondrites are chemically primitive and carbonaceous (C) chondrites are potentially the most primitive among them because they mostly escaped thermal metamor-phism that affected the other chondrite groups and ratios of their major, non-volatile and most of the volatile elements are similar to those of the Sun. Therefore, C chondrites are ex-pected to retain a good record of the origin and early history of the solar system. Carbonaceous chondrites are chemically differentiated from other chondrites by their high Mg/Si ratios and refractory elements, and have experienced various degrees of aqueous alteration. They are subdivided into eight subgroups (CI, CM, CO, CV, CK, CR, CB and CH) based on major element and oxygen isotopic ratios. Their elemental ratios spread over a wide range though those of ordinary and enstatite chondrites are relatively uniform. It is critical to know how many sepa-rate bodies are represented by the C chondrites. In this study, CM chondrites, the most abundant carbona-ceous chondrites, are examined. They are water-rich, chon-drule- and CAI-bearing meteorites and most of them are brec-cias. High-temperature components such as chondrules, iso-lated olivine and CAIs in CMs are frequently altered and some of them are replaced by clay minerals and surrounded by sul-fides whose Fe was derived from mafic silicates. On the basis of degrees of aqueous alteration, CMs have been classified into subtypes from 1 to 2, although Rubin et al. [1] assigned subtype 1 to subtype 2 and subtype 2 to subtype 2.6 using various petrologic properties. The classification is based on petrographic and mineralogic properties. For example, though tochilinite (2[(Fe, Mg, Cu, Ni[])S] 1.57-1.85 [(Mg, Fe, Ni, Al, Ca)(HH)2]) clumps are produced during aqueous alteration, they disappear and sulfide appears with increasing degrees of aqueous alteration. Cosmic-ray exposure (CRE) age measurements of CM chondrites reveal an unusual feature. Though CRE ages of other chondrite groups range from several Myr to tens of Myr, CMs exposure ages are not longer than 7 Myr with one-third of the CM having less than 1 Myr CRE age. For those CM chondrites that have CRE ages <1 Myr, there are two discern-able CRE peaks. Because a CRE age reflects how long a me-teorite is present as a separate body in space, the peaks pre-sumably represent collisional events on the parent body (ies) [2]. In this study we defined 4 distinct CRE age groups of CMs and systematically characterized the petrography in each of the 4 CRE age groups to determine whether the groups have significant petrographic differences, with such differences probably reflecting different parent body (asteroid) geological processing, or multiple original bodies.

Takenouchi, A.↗

CM Carbonaceous Chondrite Lithologies and Their Space Exposure Ages

The CMs are the most commonly falling C chondrites, and therefore may be a major component of C-class asteroids, the targets of several current and future space missions. Previous work [1] has concluded that CM chondrites fall into at least four distinct cosmic ray space exposure (CRE) age groups (0.1 million years, 0.2 million years, 0.6 million years and greater than 2.0 million years), an unusually large number, but the meaning of these groupings is unclear. It is possible that these meteorites came from different parent bodies which broke up at different times, or instead came from the same parent body which underwent multiple break-up events, or a combination of these scenarios, or something else entirely. The objective of this study is to investigate the diversity of lithologies which make up CM chondrites, in order to determine whether the different exposure ages correspond to specific, different CM lithologies, which permit us to constrain the history of the CM parent body(ies). We have already reported significant petrographic differences among CM chondrites [2-4]. We report here our new results.

Zolensky, Michael↗

Abundant Extraterrestrial Amino Acids in the Primitive CM Carbonaceous Chondrite Asuka 12236

The Asuka (A)-12236 meteorite has recently been classified as a CM carbonaceous chondrite of petrologic type 3.0/2.9 and is among the most primitive CM meteorites studied to date. Here, we report the concentrations, relative distributions, and enantiomeric ratios of amino acids in water extracts of the A-12236 meteorite and another primitive CM chondrite Elephant Moraine(EET) 96029 (CM2.7) determined by ultra-high-performance liquid chromatography time-of-flight mass spectrometry. EET 96029 was highly depleted in amino acids and dominated by glycine, while a wide diversity of two- to six-carbon aliphatic primary amino acids were identified in A-12236, which had a total amino acid abundance of 360 ± 18 nmol g-1, with most amino acids present without hydrolysis (free). The amino acid concentrations of A-12236 were double those previously measured in the CM2.7 Paris meteorite, consistent with A-12236 being a highly primitive and unheated CM chondrite. The high relative abundance of α-amino acids in A-12236 are consistent with formation by a Strecker-cyanohydrin dominated synthesis during a limited early aqueous alteration phase on the CM meteorite parent body. The presence of predominantly free glycine, a near racemic mixture of alanine (D/L ~0.93 to 0.96), and elevated abundances of several terrestrially rare non-protein amino acids including α-amino isobutyric acid (α-AIB) and racemic isovaline, indicate that these amino acids in A-12236 are extraterrestrial in origin. Given a lack of evidence for biological amino acid contamination in A-12236, it is possible that some of the L-enantiomeric excesses (Lee ~34 to 64%) of the protein amino acids aspartic and glutamic acids and serine are indigenous to the meteorite; however, isotopic measurements are needed for confirmation. In contrast to more aqueously altered CMs of petrologic types ≤ 2.5, no L-isovaline excesses were detected in A-12236. This observation strengthens the hypothesis that extensive parent body aqueous activity is required to produce or amplify the large L-isovaline excesses that cannot be explained solely by exposure to circularly polarized radiation or other chiral symmetry breaking mechanisms prior to incorporation into the asteroid parent body.

Daniel P Glavin↗

PWM for Simultaneous Minimization of Switching Losses and CM Voltage in Current Source Inverters

This article proposes a new pulsewidth modulation (PWM) scheme that reduces common-mode (CM) voltage and switching losses simultaneously in CSI. The proposed PWM [i.e., reduced voltages PWM (RVM)] reduces CM voltages and switching losses by selecting the optimal zero current vector and PWM sequence based on the CSI output voltage conditions. This article also proves the proposed RVM achieves both objectives (i.e., reduced CM voltage and switching losses) simultaneously for all CSI operating conditions without compromising the other objective. The proposed RVM inherently achieves zero-voltage switching (ZVS) conditions during the zero current vector transitions, further reducing the switching losses. Experimental results demonstrate significant reductions in CM voltage, reaching up to approximately 95%, accompanied by an increase of up to about 5.5% in CSI efficiency across a wide operating range compared to alternative PWM methods, confirming the predicted advantages of the proposed RVM.

42 ENGINEERING↗

Extraterrestrial Hydroxy Amino Acids in CM and CR Carbonaceous Chondrites

7 The abundances, distributions, and enantiomeric ratios of a family of three- and four- 8 9 10 carbon hydroxy amino acids (HAAs) were investigated in extracts of five CM and four 11 12 13 CR carbonaceous chondrites by gas chromatography-mass spectrometry (GC-MS) 14 15 16 analyses. Hydroxy amino acids were detected in both the acid hydrolysates of the hot 17 18 19 water extracts and the 6 M HCl extracts of all the CM and CR chondrites analyzed 20 21 22 here with total hot water and HCl extractable HAA concentrations ranging from 6.94 23 24 25 to 315 nmol per gram. The HAA analyses performed in this study revealed: 1) the 26 27 28 combined (hot water + HCl) extracts of CR2 chondrites contained greater abundances 29 30 31 of -HAAs than that of CM2 chondrites and 2) the combined extracts of CM and CR 32 33 34 chondrites contained roughly similar abundances of β- and γ-HAAs. Application of the 35 36 37 new GC-MS method developed here resulted in the first successful chromatographic 38 39 40 resolution of the enantiomers of an -dialkyl HAA, D,L--methylserine, in 41 42 43 carbonaceous chondrite extracts. Meteoritic -methylserine was found to be mostly 44 45 46 racemic within error and did not show L-enantiomeric excesses correlating with the 47 48 49 degree of aqueous alteration, a phenomenon observed in meteoritic isovaline, another 50 51 52 -dialkyl amino acid. The HAAs identified in CM and CR chondrite extracts could have 53 54 55 been produced during parent body alteration from the Strecker cyanohydrin reaction 56 57 58 (for -HAAs) and an ammonia-involved formose-like reaction (for β-, and γ-HAAs).

Amino acid(s), CM carbonaceous chondrite < Meteori↗

Extraterrestrial hydroxy amino acids in CM and CR carbonaceous chondrites

The abundances, distributions, and enantiomeric ratios of a family of three- and four-carbon hydroxy amino acids (HAAs) were investigated in extracts of five CM and four CR carbonaceous chondrites by gas chromatography-mass spectrometry analyses. HAAs were detected in both the acid hydrolysates of the hot water extracts and the 6 M HCl extracts of all the CM and CR chondrites analyzed here with total hot water and HCl extractable HAA concentrations ranging from 6.94 to 315 nmol/g. The HAA analyses performed in this study revealed: (1) the combined (hot water + HCl) extracts of CR2 chondrites contained greater abundances of α-HAAs than that of CM2 chondrites and (2) the combined extracts of CM and CR chondrites contained roughly similar abundances of β- and γ-HAAs. Application of the new GC-MS method developed here resulted in the first successful chromatographic resolution of the enantiomers of an α-dialkyl HAA, d,l-α-methylserine, in carbonaceous chondrite extracts. Meteoritic α-methylserine was found to be mostly racemic within error and did not show l-enantiomeric excesses correlating with the degree of aqueous alteration, a phenomenon observed in meteoritic isovaline, another α-dialkyl amino acid. The HAAs identified in CM and CR chondrite extracts could have been produced during parent body alteration from the Strecker cyanohydrin reaction (for α-HAAs) and an ammonia-involved formose-like reaction (for β-, and γ-HAAs).

Amino acid(s)↗

Remote quantification of Cm(III) and HNO 3 by fluorescence spectroscopy and chemometrics

A unique approach to remotely quantify Cm(III) (0–100 µg mL −1 ) in HNO 3 (1–12 M) using steady-state laser fluorescence spectroscopy and multivariate regression models was developed. Photoluminescence is amenable to remote measurements using fiber-optic cables and is sensitive to numerous lanthanide and actinide species. In-line measurements can provide feedback to support complex processing in harsh environments (e.g., hot cells) to help guide and optimize radiochemical separations. In this work, Cm(III) spectra were acquired remotely in a glove box as a function of HNO 3 concentration to better understand spectral characteristics and evaluate the utility of multivariate regression models in this system. Furthermore, the Cm(III) fluorescence peak shape, width, position, and intensity changed significantly as a function of HNO 3 concentration, likely because of the displacement of emission quenching inner-sphere water molecules and complexation with nitrate ions. Despite significant covariance and nonlinearity in the data, a D-optimal design strategy successfully minimized training set sample size and was used to build effective partial least squares regression models for Cm(III) and HNO 3 concentrations without a priori knowledge of solution conditions. Chemometrics for modeling complex fluorescence spectra are promising and may find widespread applicability for online analysis in numerous chemical systems found in the nuclear field.

Actinide↗

Molten Sodium Penetration in NaSICON Electrolytes at 0.1 A cm –2

High-conductivity solid electrolytes, such as the Na superionic conductor, NaSICON, are poised to play an increasingly important role in safe, reliable battery-based energy storage, enabling advanced sodium-based batteries. Coupled demands of increased current density (≥0.1 A cm –2 ) and low-temperature (<200 °C) operation, combined with increased discharge times for long-duration storage (>12 h), challenge the limitations of solid electrolytes. Here, we explore the penetration of molten sodium into NaSICON at high current densities. Previous studies of β"-alumina proposed that Poiseuille pressure-driven cracking (mode I) and recombination of ions and electrons within the solid electrolyte (mode II) are the two main mechanisms for Na penetration, but a comprehensive study of Na penetration in NaSICON is necessary, particularly at high current density. To further understand these modes, this work employs unidirectional galvanostatic testing of Na|NaSICON|Na symmetric cells at 0.1 A cm –2 over 23 h at 110 °C. Further, while galvanostatic testing shows a relatively constant yet increasingly noisy voltage profile, electrochemical impedance spectroscopy (EIS) reveals a significant decrease in cell impedance correlated with significant sodium penetration, as observed in scanning electron microscopy (SEM). Further SEM analysis of sodium accumulation within NaSICON suggests that mode II failure may be far more prevalent than previously considered. Further, these findings suggest that total (dis)charge density (mAh cm –2 ), as opposed to current density (mA cm –2 ), may be a more critical parameter when examining solid electrolyte failure, highlighting the challenge of achieving long discharge times in batteries using solid electrolytes. Together, these results provide a better understanding of the limitations of NaSICON solid electrolytes under high current and emphasize the need for improved electrode–electrolyte interfaces.

25 ENERGY STORAGE↗

A generative modeling approach to reconstructing 21 cm tomographic data

Abstract Analyses of the cosmic 21 cm signal are hampered by astrophysical foregrounds that are far stronger than the signal itself. These foregrounds, typically confined to a wedge-shaped region in Fourier space, often necessitate the removal of a vast majority of modes, thereby degrading the quality of the data anisotropically. To address this challenge, we introduce a novel deep generative model based on stochastic interpolants to reconstruct the 21 cm data lost to wedge filtering. Our method leverages the non-Gaussian nature of the 21 cm signal to effectively map wedge-filtered 3D lightcones to samples from the conditional distribution of wedge-recovered lightcones. We demonstrate how our method is able to restore spatial information effectively, considering both varying cosmological initial conditions and astrophysics. Furthermore, we discuss a number of future avenues where this approach could be applied in analyses of the 21 cm signal, potentially offering new opportunities to improve our understanding of the Universe during the epochs of cosmic dawn and reionization. Code, pre-trained models, and scripts for making plots in this paper can be found here .

Sabti, Nashwan (ORCID:000000027924546X)↗

H i 21-cm absorption in radio-loud AGN with double-peaked [O iii ] emission

ABSTRACT Different physical processes in galaxy evolution, such as galaxy mergers that lead to coalescence of dual Active Galactic Nuclei (AGN) and outflows emanating from the narrow line region, can leave their imprint on the optical spectra of AGN in the form of double-peaked narrow emission lines. To investigate the neutral gas in the centres of such AGN, we have conducted a pilot survey of H i 21-cm absorption, using the upgraded Giant Metrewave Radio Telescope (uGMRT), in radio-loud AGN whose optical spectra show double-peaked [O iii] emission lines at z ≤ 0.4 (median z ≈ 0.14). Among the eight sources for which we could obtain clean spectra, we detect H i 21-cm absorption in three sources (detection rate of $38^{+36}_{-20}$ per cent) and find tentative indication of absorption in two other sources. The detection rate of H i 21-cm absorption is tentatively higher for the systems that show signatures of interaction or tidal disturbance (≳ 50 per cent) in the ground-based optical images than that for the systems that appear single and undisturbed (≈25 per cent). This is consistent with the high incidence of H i 21-cm absorption observed in z ≤ 0.2 galaxy mergers. Higher spatial resolution spectroscopy is required to confirm the origin of the H i absorbing gas, i.e. either gas infalling on to the radio-loud AGN, outflowing gas ejected by the AGN, or gas in rotation on the galactic-scale or circumnuclear discs.

79 ASTRONOMY AND ASTROPHYSICS↗

Inhomogeneous energy injection in the 21-cm power spectrum: Sensitivity to dark matter decay

The 21-cm signal provides a novel avenue to measure the thermal state of the Universe during cosmic dawn and reionization (redshifts z ~ 5–30), and thus to probe energy injection from decaying or annihilating dark matter (DM). These DM processes are inherently inhomogeneous: both decay and annihilation are density-dependent, and furthermore, the fraction of injected energy that is deposited at each point depends on the gas ionization and density, leading to further anisotropies in absorption and propagation. In this work, we develop a new framework for modeling the impact of spatially inhomogeneous energy injection and deposition during cosmic dawn, accounting for ionization and baryon density dependence, as well as the attenuation of propagating photons. We showcase how this first completely inhomogeneous treatment affects the predicted 21-cm power spectrum in the presence of exotic sources of energy injection, and forecast the constraints that upcoming HERA measurements of the 21-cm power spectrum will set on DM decays to photons and to electron/positron pairs. These projected constraints considerably surpass those derived from CMB and Lyman-a measurements, and for decays to electron/positron pairs they exceed all existing constraints in the sub-GeV mass range, reaching lifetimes of ~10 28 s. Our analysis demonstrates the unprecedented sensitivity of 21-cm cosmology to exotic sources of energy injection during the cosmic dark ages. Our code, dm21cm, includes all these effects and is publicly available in an accompanying release.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Full-Scale Assembly 30 cm Drop Test

Can Spent Nuclear Fuel withstand the shocks and vibrations experienced during normal conditions of transport? This question was the motivation for the multi-modal transportation test (MMTT) (Summer 2017), 1/3-scale cask 30 cm drop test (December 2018), and full-scale assembly 30 cm drop tests (June 2019). The full-scale ENSA ENUN 32P cask with 3 surrogate 17x17 PWR assemblies was used in the MMTT. The 1/3-scale cask was a mockup of this cask. The 30 cm drop tests provided the accelerations on the 1/3-scale dummy assemblies. These data were used to design full-scale assembly drop tests with the goal to quantify the strain fuel rods experience inside a cask when dropped from a height of 30 cm. The drop tests were first done with the dummy and then with the surrogate assembly. This paper presents the preliminary results of the tests.

Transportation↗

On The Deflagration to Detonation Transition in 1.65 g cm -3 Pentaerythritol Tetranitrate

The LANL Weapons Response Group is charged with making determinations for a wide range of scenarios regarding the probability that inadvertent ignition of the high explosive (HE) components might cause nuclear yield, or dispersal of special nuclear material, during assembly/disassembly operations at the Pantex Plant. These scenarios are categorized based on the nature of the ignition causing stimulus, i.e. impact, electrostatic discharge, pressure-shear, etc. However, for all of these scenarios, regardless of how ignition is achieved, there must also be a credible path for the burning HE to transition to detonation for yield or dispersal to occur. If it can be determined that there is no feasible path for deflagration-to-detonation transition (DDT), the scenario space that requires mitigative action is greatly reduced. The strategy to support Weapons Response determinations is to use experimentation and observation to evaluate HE response in severe “overtest” configurations. To increase with confidence in the margins of HE response, these overtests are designed, by controlling parameters known to enhance HE response violence, to be more severe than what is ever encountered in the actual operations environment at the Plant. This study is focused on DDT in pentaerythritol tetranitrate (PETN), a high explosive that is used in LANL’s detonators. PETN is known to be able to DDT at certain densities, and this represents a safety concern. The PETN in LANL’s detonators is commonly a density of 1.65 g cm -3 . However, DDT has never been observed at this density in PETN. In this work, we studied the DDT reaction in 1.65 g cm -3 PETN to determine whether DDT is possible at this density, and if so, what length of PETN is required for the transition to occur. In any of the tests conducted, we did not observe DDT in 1.65 g cm -3 PETN. It is possible that the DDT length for 1.65 g cm -3 PETN is greater than 6” (the available run length in the experiments), but this length is simply not available in a detonator, and is therefore not a concern.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗

Eu(III) and Cm(III) Complexation by the Aminocarboxylates NTA, EDTA, and EGTA Studied with NMR, TRLFS, and ITC—An Improved Approach to More Robust Thermodynamics

The complex formation of Eu(III) and Cm(III) was studied via tetradentate, hexadentate, and octadentate coordinating ligands of the aminopolycarboxylate family, viz., nitrilotriacetate (NTA 3- ), ethylenediaminetetraacetate (EDTA 4- ), and ethylene glycol-bis(2-aminoethyl ether)-N,N,N',N'-tetraacetate (EGTA 4- ), respectively. Based on the complexones’ pK a values obtained from 1 H nuclear magnetic resonance (NMR) spectroscopic pH titration, complex formation constants were determined by means of the parallel-factor-analysis-assisted evaluation of Eu(III) and Cm(III) time-resolved laser-induced fluorescence spectroscopy (TRLFS). This was complemented by isothermal titration calorimetry (ITC), providing the enthalpy and entropy of the complex formation. This allowed us to obtain genuine species along with their molecular structures and corresponding reliable thermodynamic data. The three investigated complexones formed 1:1 complexes with both Eu(III) and Cm(III). Besides the established Eu(III)–NTA 1:1 and 1:2 complexes, we observed, for the first time, the existence of a Eu(III)–NTA 2:2 complex of millimolar metal and ligand concentrations. Demonstrated for thermodynamic studies on Eu(III) and Cm(III) interaction with complexones, the utilized approach is commonly applicable to many other metal–ligand systems, even to high-affinity ligands.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗