Separation of protactinium from uranium-niobium alloys for 231Pa-235U radiochronometry in nuclear forensic investigations.

The isolation and purification of protactinium from uranium materials is essential for 231Pa-235U radiochronometry, but separating Pa from uranium-niobium alloys, a common material in the nuclear fuel cycle, is challenging due to the chemical similarity of Pa and Nb. Here we present three resin chromatography separation techniques for isolating Pa from U and Nb which were independently developed by three different laboratories through ad hoc adaptations of standard operating procedures. Our results underscore the need for and value of purification methods suitable for a diversity of uranium-based materials to ensure the operational readiness of nuclear forensics laboratories. Supplementary Information: The online version contains supplementary material available at 10.1007/s10967-023-08928-y.

Trace Actinide Signatures of a Bulk Neptunium Sample.

In nuclear forensic analyses, measurements of actinide elements in a sample can assist with identifying interdicted or unknown materials. While these radiochemical signatures have been extensively investigated in uranium materials, less is known about bulk neptunium samples. This paper describes the measurement of trace actinide concentrations and isotopic profiles in a 237Np oxide sample. Uranium, plutonium, americium, and curium concentrations and isotopic profiles in the sample were determined and deemed potentially useful for distinguishing different sources of 237Np. Several different potential radiochronometry systems were also investigated; discordant results indicate that the Np sample was never completely purified of other actinide elements, or that subsequent contamination of the sample occurred. Few prior studies of neptunium materials have been reported, and these data suggest that trace actinide constituents could provide unique signatures to identify material out of regulatory control.

Nuclear Sample Provenance and Age Determination Using Ruthenium Isotopes.

Measurements of the ruthenium isotopic composition of nuclear samples could provide information about the method of sample production, sample irradiation history, and age. To investigate the feasibility and applicability of this idea, this study focuses on measurements of the ruthenium isotope composition of a nominally single-isotope 106Ru radioactivity standard, where the complications of environmental mixing are eliminated. The measurements of the 106Ru standards reveal unusual stable ruthenium isotopic compositions consistent with fissiogenic ruthenium. Three different lots of the material have been investigated, and the isotopic composition is found to be different for lot 1 as compared to lots 2 and 3, indicating a longer irradiation duration incurred during the production of lot 1. Through measurements of 106Ru and its 106Pd daughter, radiochronometry can be used to infer the ages of the samples. Lot 1 is older than lots 2 and 3 and was produced 4.91(5) years before the reference date of 1/1/21, approximately 2.7 years before lots 2 and 3. In an effort to better understand the sample production pathway, the isotopic measurements are compared with nuclear reactor simulations, which suggest that the material was generated by irradiation of a low-enriched uranium target material in a light water reactor. These findings have significant implications for nuclear treaty monitoring, providing an example of the power of ruthenium isotope measurements to discern details of sample origin and history.

The impact and recovery of asteroid 2018 LA.

The June 2, 2018, impact of asteroid 2018 LA over Botswana is only the second asteroid detected in space prior to impacting over land. Here, we report on the successful recovery of meteorites. Additional astrometric data refine the approach orbit and define the spin period and shape of the asteroid. Video observations of the fireball constrain the asteroid's position in its orbit and were used to triangulate the location of the fireball's main flare over the Central Kalahari Game Reserve. 23 meteorites were recovered. A consortium study of eight of these classifies Motopi Pan as a HED polymict breccia derived from howardite, cumulate and basaltic eucrite, and diogenite lithologies. Before impact, 2018 LA was a solid rock of ~156 cm diameter with high bulk density ~2.85 g/cm3, a relatively low albedo pv ~ 0.25, no significant opposition effect on the asteroid brightness, and an impact kinetic energy of ~0.2 kt. The orbit of 2018 LA is consistent with an origin at Vesta (or its Vestoids) and delivery into an Earth-impacting orbit via the v6 resonance. The impact that ejected 2018 LA in an orbit towards Earth occurred 22.8 ± 3.8 Ma ago. Zircons record a concordant U-Pb age of 4563 ± 11 Ma and a consistent 207Pb/206Pb age of 4563 ± 6 Ma. A much younger Pb-Pb phosphate resetting age of 4234 ± 41 Ma was found. From this impact chronology, we discuss what is the possible source crater of Motopi Pan and the age of Vesta's Veneneia impact basin.

Trace element geochemistry of coarse-grained angrites from Northwest Africa: Implications for their petrogenesis on the angrite parent body.

The angrites are a class of achondrites that encompass a wide range of igneous textures from quenched, volcanic, and subvolcanic stones to slowly cooled, plutonic rocks. The compositions of the various geochemical reservoirs generating this variety of rocks have not been investigated fully because historically the numbers and masses of angrites available for study have been quite small. However, the rapid increase in meteorites from Northwest Africa (NWA) has enabled a renewed opportunity for such an investigation. In particular, three samples, NWA 2999, 4590, and 4801, have provided a new window into our understanding of the origin and petrogenesis of the coarse-grained (plutonic) angrites. We report here the trace element abundances in individual mineral grains of pyroxene, plagioclase, olivine/kirschsteinite, and phosphate and in the whole-rock samples. We utilize these data to constrain the petrogenetic history of each of these samples on the angrite parent body (e.g., parental melt compositions and oxygen fugacity conditions) and assess genetic relationships to previously investigated angrites. The trace element abundances in each of the three coarse-grained angrites studied here indicate a unique history for each. The observed trace element abundances and patterns in NWA 2999 show similarities with previously studied fine-grained, volcanic angrites and potentially indicate a common geochemical source reservoir, even though NWA 2999 is temporally distinct from the volcanic angrites. In contrast, NWA 4590 has trace element characteristics analogous to other coarse-grained angrites (e.g., Lewis Cliff [LEW] 86010), suggesting that these samples originated from geochemically similar source reservoirs. The third angrite, NWA 4801, exhibits geochemical characteristics most similar to the plutonic, coarse-grained angrites, but also appears to have some affinities in its trace element characteristics to the volcanic, fine-grained angrites. This suggests that NWA 4801 may represent a petrogenetic link between two distinct geochemical reservoirs on the angrite parent body. In aggregate, the trace element distributions in these three plutonic angrites suggest that while they may have originated up to several million years after the fine-grained angrites, they sampled a range of source reservoirs on the angrite parent body. Some of these source reservoirs were likely similar to those of the fine-grained angrites, but others had distinct geochemical characteristics.

Chromium Isotopic Evidence for Mixing of NC and CC Reservoirs in Polymict Ureilites: Implications for Dynamical Models of the Early Solar System.

Nucleosynthetic isotope anomalies show that the first few million years of solar system history were characterized by two distinct cosmochemical reservoirs, CC (carbonaceous chondrites and related differentiated meteorites) and NC (the terrestrial planets and all other groups of chondrites and differentiated meteorites), widely interpreted to correspond to the outer and inner solar system, respectively. At some point, however, bulk CC and NC materials became mixed, and several dynamical models offer explanations for how and when this occurred. We use xenoliths of CC materials in polymict ureilite (NC) breccias to test the applicability of such models. Polymict ureilites represent regolith on ureilitic asteroids but contain carbonaceous chondrite-like xenoliths. We present the first 54Cr isotope data for such clasts, which, combined with oxygen and hydrogen isotopes, show that they are unique CC materials that became mixed with NC materials in these breccias. It has been suggested that such xenoliths were implanted into ureilites by outer solar system bodies migrating into the inner solar system during the gaseous disk phase ~3-5 Myr after CAI, as in the "Grand Tack" model. However, combined textural, petrologic, and spectroscopic observations suggest that they were added to ureilitic regolith at ~50-60 Myr after CAI, along with ordinary, enstatite, and Rumuruti-type chondrites, as a result of breakup of multiple parent bodies in the asteroid belt at this time. This is consistent with models for an early instability of the giant planets. The C-type asteroids from which the xenoliths were derived were already present in inner solar system orbits.

Chondrules reveal large-scale outward transport of inner Solar System materials in the protoplanetary disk.

Dynamic models of the protoplanetary disk indicate there should be large-scale material transport in and out of the inner Solar System, but direct evidence for such transport is scarce. Here we show that the ε50Ti-ε54Cr-Δ17O systematics of large individual chondrules, which typically formed 2 to 3 My after the formation of the first solids in the Solar System, indicate certain meteorites (CV and CK chondrites) that formed in the outer Solar System accreted an assortment of both inner and outer Solar System materials, as well as material previously unidentified through the analysis of bulk meteorites. Mixing with primordial refractory components reveals a "missing reservoir" that bridges the gap between inner and outer Solar System materials. We also observe chondrules with positive ε50Ti and ε54Cr plot with a constant offset below the primitive chondrule mineral line (PCM), indicating that they are on the slope ∼1.0 in the oxygen three-isotope diagram. In contrast, chondrules with negative ε50Ti and ε54Cr increasingly deviate above from PCM line with increasing δ18O, suggesting that they are on a mixing trend with an ordinary chondrite-like isotope reservoir. Furthermore, the Δ17O-Mg# systematics of these chondrules indicate they formed in environments characterized by distinct abundances of dust and H2O ice. We posit that large-scale outward transport of nominally inner Solar System materials most likely occurred along the midplane associated with a viscously evolving disk and that CV and CK chondrules formed in local regions of enhanced gas pressure and dust density created by the formation of Jupiter.

The fall, recovery, classification, and initial characterization of the Hamburg, Michigan H4 chondrite.

The Hamburg meteorite fell on January 16, 2018, near Hamburg, Michigan, after a fireball event widely observed in the U.S. Midwest and in Ontario, Canada. Several fragments fell onto frozen surfaces of lakes and, thanks to weather radar data, were recovered days after the fall. The studied rock fragments show no or little signs of terrestrial weathering. Here, we present the initial results from an international consortium study to describe the fall, characterize the meteorite, and probe the collision history of Hamburg. About 1 kg of recovered meteorites was initially reported. Petrology, mineral chemistry, trace element and organic chemistry, and O and Cr isotopic compositions are characteristic of H4 chondrites. Cosmic ray exposure ages based on cosmogenic 3He, 21Ne, and 38Ar are ~12 Ma, and roughly agree with each other. Noble gas data as well as the cosmogenic 10Be concentration point to a small 40-60 cm diameter meteoroid. An 40Ar-39Ar age of 4532 ± 24 Ma indicates no major impact event occurring later in its evolutionary history, consistent with data of other H4 chondrites. Microanalyses of phosphates with LA-ICPMS give an average Pb-Pb age of 4549 ± 36 Ma. This is in good agreement with the average SIMS Pb-Pb phosphate age of 4535.3 ± 9.5 Ma and U-Pb Concordia age of 4535 ± 10 Ma. The weighted average age of 4541.6 ± 9.5 Ma reflects the metamorphic phosphate crystallization age after parent body formation in the early solar system.

The origin of the unique achondrite Northwest Africa 6704: Constraints from petrology, chemistry and Re-Os, O and Ti isotope systematics.

Northwest Africa (NWA) 6704 is a unique achondrite characterized by a near-chondritic major element composition with a remarkably intact igneous texture. To investigate the origin of this unique achondrite, we have conducted a combined petrologic, chemical, and 187Re-187Os, O, and Ti isotopic study. The meteorite consists of orthopyroxene megacrysts (En55-57Wo3-4Fs40-42; Fe/Mn = 1.4) up to 1.7 cm in length with finer interstices of olivine (Fa50-53; Fe/Mn = 1.1-2.1), chromite (Cr# ~ 0.94), awaruite, sulfides, plagioclase (Ab92An5Or3) and merrillite. The results of morphology, lattice orientation analysis, and mineral chemistry indicate that orthopyroxene megacrysts were originally hollow dendrites that most likely crystallized under high super-saturation and super-cooling conditions (1-102 °C/h), whereas the other phases crystallized between branches of the dendrites in the order of awaruite, chromite → olivine → merrillite → plagioclase. In spite of the inferred high supersaturation, the remarkably large size of orthopyroxene can be explained as a result of crystallization from a melt containing a limited number of nuclei that are preserved as orthopyroxene megacryst cores having high Mg# or including vermicular olivine. The Re-Os isotope data for bulk and metal fractions yield an isochron age of 4576 ± 250 Ma, consistent with only limited open system behavior of highly siderophile elements (HSE) since formation. The bulk chemical composition is characterized by broadly chondritic absolute abundances and only weakly fractionated chondrite-normalized patterns for HSE and rare earth elements (REE), together with substantial depletion of highly volatile elements relative to chondrites. The HSE and REE characteristics indicate that the parental melt and its protolith had not undergone significant segregation of metals, sulfides, or silicate minerals. These combined results suggest that a chondritic precursor to NWA 6704 was heated well above its liquidus temperature so that highly volatile elements were lost and the generated melt initially contained few nuclei of relict orthopyroxene, but the melting and subsequent crystallization took place on a timescale too short to allow magmatic differentiation. Such rapid melting and crystallization might occur as a result of impact on an undifferentiated asteroid. The O-Ti isotope systematics (Δ17O = -1.052 ± 0.004, 2 SD; ε50Ti = 2.28 ± 0.23, 2 SD) indicate that the NWA 6704 parent body sampled the same isotopic reservoirs in the solar nebula as the carbonaceous chondrite parent bodies. This is consistent with carbonaceous chondrite-like refractory element abundances and oxygen fugacity (FMQ = -2.6) in NWA 6704. Yet, the Si/Mg ratio of NWA 6704 is remarkably higher than those of carbonaceous chondrites, suggesting significant nebular fractionation of forsterite in its provenance.

Petrogenesis and Provenance of Ungrouped Achondrite Northwest Africa 7325 from Petrology, Trace Elements, Oxygen, Chromium and Titanium Isotopes, and Mid-IR Spectroscopy.

Northwest Africa (NWA) 7325 is an ungrouped achondrite that has recently been recognized as a sample of ancient differentiated crust from either Mercury or a previously unknown asteroid. In this work we augment data from previous investigations on petrography and mineral compositions, mid-IR spectroscopy, and oxygen isotope compositions of NWA 7325, and add constraints from Cr and Ti isotope compositions on the provenance of its parent body. In addition, we identify and discuss notable similarities between NWA 7325 and clasts of a rare xenolithic lithology found in polymict ureilites. NWA 7325 has a medium grained, protogranular to poikilitic texture, and consists of 10-15 vol. % Mg-rich olivine (Fo 98), 25-30 vol. % diopside (Wo 45, Mg# 98), 55-60 vol. % Ca-rich plagioclase (An 90), and trace Cr-rich sulfide and Fe,Ni metal. We interpret this meteorite to be a cumulate that crystallized at ≥1200 °C and very low oxygen fugacity (similar to the most reduced ureilites) from a refractory, incompatible element-depleted melt. Modeling of trace elements in plagioclase suggests that this melt formed by fractional melting or multi-stage igneous evolution. A subsequent event (likely impact) resulted in plagioclase being substantially remelted, reacting with a small amount of pyroxene, and recrystallizing with a distinctive texture. The bulk oxygen isotope composition of NWA 7325 plots in the range of ureilites on the CCAM line, and also on a mass-dependent fractionation line extended from acapulcoites. The ε54Cr and ε50Ti values of NWA 7325 exhibit deficits relative to terrestrial composition, as do ordinary chondrites and most achondrites. Its ε54Cr value is distinct from that of any analyzed ureilite, but is not resolved from that of acapulcoites (as represented by Acapulco). In terms of all these properties, NWA 7325 is unlike any known achondrite. However, a rare population of clasts found in polymict ureilites ("the magnesian anorthitic lithology") are strikingly similar to NWA 7325 in mineralogy and mineral compositions, oxygen isotope compositions, and internal textures in plagioclase. These clasts are probably xenolithic in polymict ureilites, and could be pieces of NWA 7325-like meteorites. Using constraints from chromium, titanium and oxygen isotopes, we discuss two possible models for the provenance of the NWA 7325 parent body: 1) accretion in the inner solar system from a reservoir similar to that of acapulcoites in Δ17O, ε54Cr and ε50Ti; or 2) early (< 1 Ma after CAI formation) accretion in the outer solar system (beyond the snow line), before 54Cr and 50Ti anomalies were introduced to this region of the solar system. The mid-IR emission spectrum of NWA 7325 obtained in this work matches its modal mineralogy, and so can be compared with spectra of new meteorites or asteroids/planets to help identify similar materials and/or the parent body of NWA 7325.

Chelyabinsk airburst, damage assessment, meteorite recovery, and characterization.

The asteroid impact near the Russian city of Chelyabinsk on 15 February 2013 was the largest airburst on Earth since the 1908 Tunguska event, causing a natural disaster in an area with a population exceeding one million. Because it occurred in an era with modern consumer electronics, field sensors, and laboratory techniques, unprecedented measurements were made of the impact event and the meteoroid that caused it. Here, we document the account of what happened, as understood now, using comprehensive data obtained from astronomy, planetary science, geophysics, meteorology, meteoritics, and cosmochemistry and from social science surveys. A good understanding of the Chelyabinsk incident provides an opportunity to calibrate the event, with implications for the study of near-Earth objects and developing hazard mitigation strategies for planetary protection.

Fluorescence properties and photophysics of the sulfoindocyanine Cy3 linked covalently to DNA.

The sulfoindocyanine Cy3 is one of the most commonly used fluorescent dyes in the investigation of the structure and dynamics of nucleic acids by means of fluorescence methods. In this work, we report the fluorescence and photophysical properties of Cy3 attached covalently to single-stranded and duplex DNA. Steady-state and time-resolved fluorescence techniques were used to determine fluorescence quantum yields, emission lifetimes, and fluorescence anisotropy decays. The existence of a transient photoisomer was investigated by means of transient absorption techniques. The fluorescence quantum yield of Cy3 is highest when attached to the 5' terminus of single-stranded DNA (Cy3-5' ssDNA), and decreases by a factor of 2.4 when the complementary strand is annealed to form duplex DNA (Cy3-5' dsDNA). Substantial differences were also observed between the 5'-modified strands and strands modified through an internal amino-modified deoxy uridine. The fluorescence decay of Cy3 became multiexponential upon conjugation to DNA. The longest lifetime was observed for Cy3-5' ssDNA, where about 50% of the decay is dominated by a 2.0-ns lifetime. This value is more than 10 times larger than the fluorescence lifetime of the free dye in solution. These observations are interpreted in terms of a model where the molecule undergoes a trans-cis isomerization reaction from the first excited state. We observed that the activation energy for photoisomerization depends strongly on the microenvironment in which the dye is located. The unusually high activation energy measured for Cy3-5' ssDNA is an indication of dye-ssDNA interactions. In fact, the time-resolved fluorescence anisotropy decay of this sample is dominated by a 2.5-ns rotational correlation time, which evidences the lack of rotational freedom of the dye around the linker that separates it from the terminal 5' phosphate. The remarkable variations in the photophysical properties of Cy3-DNA constructs demonstrate that caution should be used when Cy3 is used in studies employing DNA conjugates.