Search Results (6)

The mass region of rare-earth nuclei in the nuclear chart is riddled with well-deformed nuclei, exhibiting rotational properties and many interesting nuclear structure-related phenomena. The scarcity of experimental data as the neutron number increases and the exotic phenomena such as shape coexistence, which are strongly connected with the underlying symmetries of the Hamiltonian and are predicted to take place in this region, make this mass region a fertile ground for experimental and theoretical studies of nuclear structure. In this work, we investigate the structure of the even–even ^162–184Hf (hafnium) isotopes through a calculation of various observables such as $B(E2;0_1^{+}\to 2_1^{+})$ reduced transition matrix elements and quadrupole moments. Six different nuclear models are employed in the calculations of the observables for these nuclei, the shapes of which deviate from spherical symmetry, and as such, are characterized by Hamiltonians, which break the rotational invariance of the exact nuclear many-body Hamiltonian. The results of the present study are expected to establish some concrete guidelines for current and future experimental endeavors. Along these lines, the results for the ^162–180Hf isotopes are compared with existing experimental data where available, showing an overall good agreement. Full article

In this paper, a boron–mannitol complex wet acid digestion method proposed for the accurate determination of boron in silicate samples by inductively coupled plasma mass spectrometry (ICP-MS) was investigated in detail for the first time. With the addition of 50 μL of mannitol (2% wt.) into the mixture of 0.6 mL of concentrated HF and 30 μL of concentrated HNO₃, the 50 mg of silicate sample was effectively decomposed after being heated overnight with optional pre-ultrasonic treatment. Following fluoride formation prevention by 8% HNO₃ (wt.) and fluoride decomposition using 6% HCl (wt.), the samples were fluxed in 2.0 mL of 40% HNO₃ (wt.) for 4 h and aged overnight. By diluting 1000-fold using 2% HNO₃ (wt.) solution, the samples were directly quantified by an ICP-MS, showing boron recoveries of the standard materials including diabase W-2, basalt JB-2a, and rhyolite JR-2 in the range of 95.5–105.5% (n = 5). For this wet acid method, it was found that the contents of boron had no obvious difference under digestion temperatures of 65, 100, and 140 °C. It was also found that the ICP-MS quantification accuracy deteriorated at the mass of ¹¹B when boron content was about 7250 ng yielding positive bias with average recoveries of 115.5–119.8% (n = 5), while the determination results remained unaffected at the mass of ¹⁰B. Furthermore, the digestion efficiency of boron by laboratory high-pressure closed digestion method was assessed. The boron recoveries with samples treated by the high-pressure closed digestion method were found to vary within 49.5–98.0% (n = 5) and even lowered down to 31.1% when skipping pressure relief procedure. The long-term quantification stability study showed that the boron content generally declined in one month for the high-pressure closed digestion method and exhibited no significant changes for the proposed method. By applying such an improved boron–mannitol complex digestion method, the boron concentration in the studied silicate standard materials were accurately determined, providing critical data for further boron isotope analyses and associated geochemical studies. This in-depth method investigation for silicate boron determination demonstrates the feasibility of this boron–mannitol complex strategy under a wide digestion temperature of 65–140 °C, and also sheds light on the extensive applications of boron as a geological tracer. Full article

Sarıcakaya–Nallıhan Volcanism was generated within the Balkanatolia Magmatic Realm between 48 and 44 Ma (by ⁴⁰Ar–³⁹Ar age determination) and is represented by three different volcanic units all displaying subduction-related geochemical signatures, such as depletion in HFSE and enrichment in LREE and LILE. The first unit (V1) consists of nepheline-normative, olivine basalts with OIB-like affinity. The second (V2) and third (V3) units are represented by more evolved compositions such as basaltic-andesitic, andesitic, and dacitic-rhyolitic lavas. Even the most basic lavas have elevated Mg# values (62–69), and they are far from representing the true mantle melts. Source characterization of Sarıcakaya–Nallıhan Volcanism reveals that there might be two possible mantle sources for the primary melts of the lavas: (i) metasomatized peridotitic mantle fluxed by sedimentary melts, or (ii) accreted mélange. The direct melting of the mélange-like lithologies is a more favorable mechanism for the Middle Eocene (44–40 Ma) magmatism in Balkanatolia since the Hf–Nd trace element, Nd isotopic systematics and petrological modelling efforts supported the latter. Overall, Early Cenozoic magmatism within this realm was characterized, first (58–44 Ma) by contractional and later (44–40 Ma) by extensional tectonics and the late-stage magmatic phase in the area was possibly controlled by melting of accreted mélange-like lithologies. The presented data indicate that mélange melting might be much more common than envisaged for the magmatism in the Alpine–Himalayan orogenic belt. Full article

We utilized the Neoma™, a recently released MC-ICP-MS platform offered by ThermoFisher Scientific, to assess the behavior of the Lu-Yb-Hf system during laser ablation analyses of various zircon standards as well as solution-based analyses of the JMC-475 Hf standard doped with varying quantities of Yb and Lu. The primary goal of this work was to characterize the behavior of the Yb interference correction on the Neoma™ platform since this is one of the biggest issues in the Hf isotope analysis community and because the Neoma™ platform will supplant the Neptune™ series instrument. During laser ablation analysis, we found that the overall data quality scales proportionally with the total Hf signal intensity, with higher signal analyses producing extremely accurate (within 1 ε_Hf unit) and precise (sub ε_Hf unit within-run standard errors) data. At low Yb signals (<0.1 V ¹⁷³Yb), we were not able to produce an accurate internal Yb mass bias factor. However, utilizing an empirical approach allows for the application of session-specific relationships between the Yb and Hf mass bias factors, determined by analysis of standards of varying Yb content, to produce accurate ε_Hf values from zircons with higher Yb/Hf ratios even where the total Hf signal intensity is relatively low. Similar behavior was observed in the solution analyses. Lastly, while the behavior of the Yb interference correction on the Neoma™ platform appears comparable to the Neptune™ series MC-ICP-MS, further work will help refine the understanding of the controls on mass bias behavior, oxide formation, session-to-session stability, etc. Full article

The Mushgai Khudag complex consists of numerous silicate volcanic-plutonic rocks including melanephelinites, theralites, trachytes, shonkinites, and syenites and also hosts numerous dykes and stocks of magnetite-apatite-enriched rocks and carbonatites. It hosts the second largest REE–Fe–P–F–Sr–Ba deposit in Mongolia, with REE mineralization associated with magnetite-apatite-enriched rocks and carbonatites. The bulk rock REE content of these two rock types varies from 21,929 to 70,852 ppm, which is much higher than that of syenites (716 ± 241 ppm). Among these, the altered magnetite-apatite-enriched rocks are characterized by the greatest level of REE enrichment (58,036 ± 13,313 ppm). Magmatic apatite from magnetite-apatite-enriched rocks is commonly euhedral with purple luminescence, and altered apatite displays variable purple to blue luminescence and shows fissures and hollows with deposition of fine-grained monazite aggregates. Most magmatic apatite within syenite is prismatic and displays oscillatory zoning with variable purple to yellow luminescence. Both magmatic and altered apatite from magnetite-apatite-enriched rocks were dated using in situ U–Pb dating and found to have ages of 139.7 ± 2.6 and 138.0 ± 1.3 Ma, respectively, which supports the presence of late Mesozoic alkaline magmatism. In situ ⁸⁷Sr/⁸⁶Sr ratios obtained for all types of apatite and calcite within carbonatite show limited variation (0.70572–0.70648), which indicates derivation from a common mantle source. All apatite displays steeply fractionated chondrite-normalized REE trends with significant LREE enrichment (46,066 ± 71,391 ppm) and high (La/Yb)_N ratios ranging from 72.7 to 256. REE contents and (La/Yb)_N values are highly variable among different apatite groups, even within the same apatite grains. The variable REE contents and patterns recorded by magmatic apatite from the core to the rim can be explained by the occurrence of melt differentiation and accompanying fractional crystallization. The Y/Ho ratios of altered apatite deviate from the chondritic values, which reflects alteration by hydrothermal fluids. Altered apatite contains a high level of REE (63,912 ± 31,785 ppm), which are coupled with increased sulfur and/or silica contents, suggesting that sulfate contributes to the mobility and incorporation of REEs into apatite during alteration. Moreover, altered apatite is characterized by higher Zr/Hf, Nb/Ta, and (La/Yb)_N ratios (179 ± 48, 19.4 ± 10.3, 241 ± 40, respectively) and a lack of negative Eu anomalies compared with magmatic apatite. The distinct chemical features combined with consistent Sr isotopes and ages for magmatic and altered apatite suggest that pervasive hydrothermal alterations at Mushgai Khudag are most probably being induced by carbonatite-evolved fluids almost simultaneously after the alkaline magmatism. Full article

We present ab-initio calculations of secondary isotope effects on NMR chemical shieldings. The change of the NMR chemical shift of a certain nucleus that is observed if another nucleus is replaced by a different isotope can be calculated by computing vibrational corrections on the NMR parameters using electronic structure methods. We demonstrate that the accuracy of the computational results is sufficient to even distinguish different conformers. For this purpose, benchmark calculations for fluoro(2-2H)ethane in gauche and antiperiplanar conformation are carried out at the HF, MP2 and CCSD(T) level of theory using basis sets ranging from double- to quadruple-zeta quality. The methodology is applied to the secondary isotope shifts for 2-fluoronorbornane in order to resolve an ambiguity in the literature on the assignment of endo- and exo-2-fluoronorbornanes with deuterium substituents in endo-3 and exo-3 positions, also yielding insight into mechanistic details of the corresponding synthesis. Full article