Stable Mo Isotopes Research Articles

Cross-Sections of Neutral-Current Neutrino Scattering on 94,96Mo Isotopes

In our recent publications, we presented neutral-current ν–nucleus cross-sections for the coherent and incoherent channels for some stable Mo isotopes, assuming a Mo detector medium, within the context of the deformed shell model. In these predictions, however, we have not included the contributions in the cross-sections stemming from the stable 94,96Mo isotopes (abundance of 94Mo 9.12% and of 96Mo 16.50%). The purpose of the present work is to perform detailed calculations of ν–94,96Mo scattering cross-sections, for a given energy Eν of the incoming neutrino, for coherent and incoherent processes. In many situations, the Eν values range from 15 to 30 MeV, and in the present work, we used Eν = 15 MeV. Mo as a detector material has been employed by the MOON neutrino and double-beta decay experiments and also from the NEMO neutrinoless double-beta decay experiment. For our cross-section calculations, we utilize the Donnelly–Walecka multipole decomposition method in which the ν–nucleus cross-sections are given as a function of the excitation energy of the target nucleus. Because only the coherent cross-section is measured by current experiments, it is worth estimating what portion of the total cross-section represents the measured coherent rate. This requires the knowledge of the incoherent cross-section, which is also calculated in the present work.

Isotopic effects on in-plane hyperbolic phonon polaritons in MoO3

Abstract Hyperbolic phonon polaritons (HPhPs), hybrids of light and lattice vibrations in polar dielectric crystals, empower nanophotonic applications by enabling the confinement and manipulation of light at the nanoscale. Molybdenum trioxide (α-MoO3) is a naturally hyperbolic material, meaning that its dielectric function deterministically controls the directional propagation of in-plane HPhPs within its reststrahlen bands. Strategies such as substrate engineering, nano- and hetero-structuring, and isotopic enrichment are being developed to alter the intrinsic dielectric functions of natural hyperbolic materials and to control the confinement and propagation of HPhPs. Since isotopic disorder can limit phonon-based processes such as HPhPs, here we synthesize isotopically enriched 92MoO3 (92Mo: 99.93 %) and 100MoO3 (100Mo: 99.01 %) crystals to tune the properties and dispersion of HPhPs with respect to natural α-MoO3, which is composed of seven stable Mo isotopes. Real-space, near-field maps measured with the photothermal induced resonance (PTIR) technique enable comparisons of in-plane HPhPs in α-MoO3 and isotopically enriched analogs within a reststrahlen band (≈820 cm−1 to ≈972 cm−1). Results show that isotopic enrichment (e.g., 92MoO3 and 100MoO3) alters the dielectric function, shifting the HPhP dispersion (HPhP angular wavenumber × thickness vs. IR frequency) by ≈−7 % and ≈+9 %, respectively, and changes the HPhP group velocities by ≈±12 %, while the lifetimes (≈3 ps) in 92MoO3 were found to be slightly improved (≈20 %). The latter improvement is attributed to a decrease in isotopic disorder. Altogether, isotopic enrichment was found to offer fine control over the properties that determine the anisotropic in-plane propagation of HPhPs in α-MoO3, which is essential to its implementation in nanophotonic applications.

In situ precise determination of stable Mo isotope ratios in molybdenite by femtosecond LA-MC-ICP-MS

We developed a new method for in situ measurement of Mo stable isotope ratios using femtosecond laser ablation coupled with MC-ICP-MS. Additionally, experiments were conducted on nine natural molybdenite samples from different ore deposits in China.

Consistent optical potential for incident and emitted low-energy α particles. III. Nonstatistical processes induced by neutrons on Zr, Nb, and Mo nuclei

The reliability of a previous $\alpha$-particle optical-model potential (OMP) on nuclei with mass number 45$\leq$$A$$\leq$209 was proved for emitted $\alpha$ particles as well, for proton--induced reactions on Zn isotopes [Phys. Rev. C {\bf 91}, 064611 (2015), Paper I]. However, the same was not the case of neutrons on Zr stable isotopes [Phys. Rev. C {\bf 96}, 044610 (2017), Paper II]. A recent assessment of this potential also for nucleon--induced $\alpha$-emission on $A$$\sim$60 nuclei, including pickup direct reaction and eventual Giant Quadrupole Resonance (GQR) $\alpha$-emission, is completed for neutrons incident on Zr, Nb, and Mo stable isotopes. Consistent sets of input parameters, determined through analysis of independent data, is involved while no further empirical rescaling factors of the $\gamma$ and nucleon widths have been involved. A suitable account of all competitive reaction channels is confirmed by careful uncertainty analysis, to avoid parameter ambiguities and/or error compensation. Additional validation of this potential is also supported by recently measured $(\alpha,\gamma)$ and $(\alpha,n)$ cross--sections of Zr and Mo nuclei. An increase of the $\alpha$-emission beyond the statistical predictions, through consideration of additional reaction channels of the pickup direct interaction and {\it like}--GQR decay, makes possible the description of both absorption and emission of $\alpha$ particles by the same optical potential.

Extreme Mo isotope variations recorded in high-SiO2 granites: Insights into magmatic differentiation and melt–fluid interaction

The Mo stable isotope system has been used to trace material recycling during subduction-related processes, but the behavior of Mo isotopes during magmatic evolution (e.g., crystal–melt fractionation and melt–fluid interaction) remains contentious, especially in high-SiO2 granites. This study addresses the issue of Mo isotope variation in high-SiO2 granites by measuring bulk-rock and mineral Mo isotopes of biotite granites (BGs) and garnet-bearing two-mica granites (GBGs) from the well-characterized Zhengga granite pluton (southern Tibet, China). The GBGs have similar Sr–Nd–O isotope compositions to those of the BGs but show higher SiO2 and lower TiO2, MgO, total Fe2O3, and CaO contents, and represent the products of advanced fractionation of the BG magmas. The BGs have lower Mo contents (0.02–0.07 ppm) and higher δ98/95Mo values (−0.54‰ to 0.22‰) compared with the GBGs (0.029–2.121 ppm and −0.97‰ to −0.41‰, respectively). Analysis of major silicate minerals suggests that substantial segregation of biotite and feldspar with high δ98/95Mo values of 0.00‰ to 0.38‰ and −1.06‰ to 0.57‰ (most within −0.58‰ to 0.13‰) could have driven the GBGs and the late-stage crystalline phase of garnet (−1.22‰ to −0.98‰) towards very low δ98/95Mo values. However, the trend of decreasing δ98/95Mo with indices of magma differentiation is not linear: one group of GBGs show increasing Mo contents and decreasing δ98/95Mo values with decreasing Y, Ho, and Dy contents; while the other group display increasing Mo contents and slightly decreasing δ98/95Mo values with respect to the increasing contents of Y, Ho, and Dy. These two contrasting behaviors can be ascribed to further crystal fractionation and melt–fluid interaction in a closed magmatic–hydrothermal system. This is also evidenced by the formation of two types of garnets with different contents of Mo and rare earth elements in these two groups of GBGs. Closed-system fluid saturation is inferred to have driven the silicate melt to be enriched in 98Mo, which limited the decrease in melt δ98/95Mo caused by crystal fractionation. These observations are supported by quantitative geochemical modeling. We conclude that both fractional crystallization and melt–fluid interaction control Mo isotope fractionation in high-SiO2 granites and that Mo isotopes are useful for tracing the evolution of high-SiO2 igneous rocks.

Radiochemical analysis of the drain water sampled at the exhaust stack shared by Units 1 and 2 of the Fukushima Daiichi Nuclear Power Station

Radioactive gas of Unit 1 of the Fukushima Daiichi Nuclear Power Station was released from the exhaust stack shared by Units 1 and 2 through the venting line on March 12th, 2011. In the present study, radiochemical analysis of drain water sampled at the drain pit of the exhaust stack was conducted to study radionuclides released during venting of the Unit 1. Not only volatile 129I, 134Cs and 137Cs but also 60Co, 90Sr, 125Sb and Unit 1-originated stable Mo isotopes were detected. Although Unit 1-originated stable Mo isotopes were clearly detected, their amounts were quite low compared to Cs, suggesting that the formation of Cs2MoO4 was suppressed under the accident condition. Approximately 90% of iodine existed as I− and 10% as IO3− in November 2020. Furthermore, larger amount of 129I than 137Cs was observed, suggesting major chemical form of 131I was molecular iodine rather than CsI at the accident time. The 134Cs/137Cs radioactivity ratio decay-corrected to March 11th, 2011 was 0.86, supported the results that Unit 1 originated radiocesium in environment has smaller 134Cs/137Cs radioactivity ratio than Unit 2 and 3 originated radiocesium.

CROSS-SECTIONS OF PHOTONUCLEAR REACTIONS ON natМо TARGETS AT END-POINT BREMSSTRAHLUNG ENERGY UP TO Еγmax = 100 МeV

Experiments to determine the yields and bremsstrahlung flux-averaged cross-sections σ(Еγmax) of photonuclear reactions on the natural Mo targets were performed on the beam from the electron linear accelerator LUE-40 with the use of the γ-activation technique. The bremsstrahlung end-point energies were in the range Еγmax = 35…80 MeV. The bremsstrahlung quantum flux was calculated with the program GEANT4.9.2 and, in addition, was monitored using the 100Мо(γ, n)99Мо reaction. Calculations of the yields and average cross-sections σ(Еγmax) for photonuclear reactions on stable Mo isotopes were computed using the σ(Е) cross-sections from the TALYS1.95 code (for the level density model LD1). A comparison of experimental and calculated cross-sections σ(Еγmax) for reactions 92Мо(γ, 2n)90Мо and 92Мо(γ, pn)90Nb was performed.

Tracing Molybdenum Attenuation in Mining Environments Using Molybdenum Stable Isotopes.

Molybdenum contamination is a concern in mining regions worldwide. Better understanding of processes controlling Mo mobility in mine wastes is critical for assessing potential impacts and developing water-quality management strategies associated with this element. Here, we used Mo stable isotope (δ98/95Mo) analyses to investigate geochemical controls on Mo mobility within a tailings management facility (TMF) featuring oxic and anoxic environments. These isotopic analyses were integrated with X-ray absorption spectroscopy, X-ray diffraction, Raman spectroscopy, transmission electron microscopy, and aqueous chemical data. Dissolved Mo concentrations were inversely correlated with δ98/95Mo values such that enrichment of heavy Mo isotopes in solution reflected attenuation processes. Inner-sphere complexation of Mo(VI) with ferrihydrite was the primary driver of Mo removal and was accompanied by a ca. 1‰ isotope fractionation. Limited Mo attenuation and isotope fractionation were observed in Fe(II)- and Mo-rich anoxic TMF seepage, while attenuation and isotope fractionation were greatest during discharge and oxidation of this seepage after discharge into a pond where Fe-(oxyhydr)oxide precipitation promoted Mo sorption. Overall, this study highlights the role of sorption onto Fe-(oxyhydr)oxides in attenuating Mo in oxic environments, a process which can be traced by Mo isotope analyses.

Aerobic iron and manganese cycling in a redox-stratified Mesoarchean epicontinental sea

Redox conditions in the marine realm prior to the Great Oxidation Event (GOE; ∼2.46–2.32 Ga ago), during which the atmospheric oxygen level rose dramatically for the first time, are still debated. Here, we present C, O, Fe, and Mo stable isotope systematics of Fe-, Mn-, and carbonate-rich shales, deposited at different water depths in association with iron formations (IFs) of the Mesoarchean Mozaan Group, Pongola Supergroup, South Africa. δ13C values between −22.3 and −13.5‰ VPDB, and δ18O values between −21.1 and −8.6‰ VPDB for Fe–Mn-rich carbonate minerals indicate their precipitation out of equilibrium with seawater. Instead, early diagenetic reduction of Fe–Mn-oxyhydroxide precursor minerals, along with microbially induced oxidation of organic matter (OM), formed these carbonates. δ56FeIRMM-014 values between −1.27 and 0.14‰ and δ98MoNIST3134+0.25 values between −0.46 and 0.56‰ co-vary with Mn concentrations and inferred water depth of deposition. This suggests that, despite the diagenetic origin of the Fe–Mn carbonates, the primary light Fe and Mo isotopic signature of Fe–Mn-oxyhydroxides that originally precipitated from seawater is still preserved. While isotopically light Mo implies that Mn(II) was oxidized to Mn(IV) due to the availability of free, photosynthetically produced O2, Mn enrichment suggests that the water column was redox stratified with a Mn-redoxcline situated at a depth below the storm wave base. A trend to highly negative δ56Fe values with increasing Mn/Fe ratios and decreasing depositional depth suggests progressive oxidation of Fe(II) as deep-waters upwelled across a redoxcline towards shallow, locally oxygenated waters where Mn(IV) oxyhydroxides precipitated. Combined δ56Fe and δ98Mo data indicate pervasive oxygenation of seawater with the O2 content in the photic zone likely reaching levels higher than the maximum value of 10 μM proposed for Archean oxygen oases. Since abiotic Mn(II) oxidation is kinetically very slow in marine environments, it is likely that Mn-oxidizing microorganisms catalyzed Mn-oxidation in the oxygenated Pongola surface waters during deposition of IFs. This implies that aerobic metabolism had evolved before the GOE in shallow, aquatic habitats, where it exerted a first-order control on the deposition of shallow-marine, Mn-rich iron formations.

I-process Contribution of Rapidly Accreting White Dwarfs to the Solar Composition of First-peak Neutron-capture Elements

Abstract Rapidly accreting white dwarfs (RAWDs) have been proposed as contributors to the chemical evolution of heavy elements in the Galaxy. Here, we test this scenario for the first time and determine the contribution of RAWDs to the solar composition of first-peak neutron-capture elements. We add the metallicity-dependent contribution of RAWDs to the one-zone galactic chemical evolution code OMEGA according to RAWD rates from binary stellar population models combined with metallicity-dependent i-process stellar yields calculated following the models of Denissenkov et al. With this approach, we find that the contribution of RAWDs to the evolution of heavy elements in the Galaxy could be responsible for a significant fraction of the solar composition of Kr, Rb, Sr, Y, Zr, Nb, and Mo ranging from 2% to 45% depending on the element, the enrichment history of the Galactic gas, and the total mass ejected per RAWD. This contribution could explain the missing solar Lighter Element Primary Process for some elements (e.g., Sr, Y, and Zr). We do not overproduce any isotope relative to the solar composition, but 96Zr is produced in a similar amount. The i process produces efficiently the Mo stable isotopes 95Mo and 97Mo. When nuclear reaction rate uncertainties are combined with our GCE uncertainties, the upper limits for the predicted RAWD contribution increase by a factor of 1.5–2 for Rb, Sr, Y, and Zr, and by 3.8 and 2.4 for Nb and Mo, respectively. We discuss the implication of the RAWD stellar evolution properties on the single-degenerate SN Ia scenario.

The Molybdenum Isotope System as a Tracer of Slab Input in Subduction Zones: An Example From Martinique, Lesser Antilles Arc

AbstractMolybdenum isotopes are fractionated by Earth‐surface processes and may provide a tracer for the recycling of crustal material into the mantle. Here, we examined the Mo isotope composition of arc lavas from Martinique in the Lesser Antilles arc, along with Cretaceous and Cenozoic Deep Sea Drilling Project sediments representing potential sedimentary inputs into the subduction zone. Mo stable isotope composition (defined as δ98Mo in ‰ deviation from the NIST 3134 standard) in lavas older than ∼7 million years (Ma) exhibits a narrow range similar to and slightly higher than MORB, whereas those younger than ∼7 Ma show a much greater range and extend to unusually low δ98Mo values. Sediments from DSDP Leg 78A, Site 543 have uniformly low δ98Mo values whereas Leg 14, Site 144 contains both sediments with isotopically light Mo and Mo‐enriched black shales with isotopically heavy Mo. When coupled with published radiogenic isotope data, Mo isotope systematics of the lavas can be explained through binary mixing between a MORB‐like end‐member and different sedimentary compositions identified in the DSDP cores. The lavas older than ∼7 Ma were influenced by incorporation of isotopically heavy black shales into the mantle wedge. The younger lavas are the product of mixing isotopically light sedimentary material into the mantle wedge. The change in Mo isotope composition of the lavas at ∼7 Ma is interpreted to reflect the removal of the Cretaceous black shale component due to the arrival of younger ocean crust where the age‐equivalent Cretaceous sediments were deposited in shallower oxic waters. Isotopic fractionation of Mo during its removal from the slab is not required to explain the observed systematics in this system.

Fraction-specific controls on the trace element distribution in iron formations: Implications for trace metal stable isotope proxies

Iron formations (IFs) are important geochemical repositories that provide constraints on atmospheric and ocean chemistry, prior to and during the onset of the Great Oxidation Event. Trace metal abundances and their Mo-Cr-U isotopic ratios have been widely used for investigating ocean redox processes through the Archean and Paleoproterozoic. Mineralogically, IFs consist of three main Fe-bearing fractions: (1) Fe-Ca-Mg-Mn carbonates, (2) magnetite and/or hematite and (3) Fe-silicates. These fractions are typically fine-grained on a sub-μm scale and their co-occurrence in varying amounts means that bulk-rock or microanalytical geochemical and stable isotope data can be influenced by cryptic changes in mineralogy. Fraction specific geochemical analysis has the potential to resolve mineralogical controls and reveal diagenetic versus primary precipitative controls on IF mineralogy. Here we adapt an existing sequential extraction scheme for Fe-phases (Poulton and Canfield, 2005) to the high Fe-content in IF and the specific three-fraction mineralogy. We optimized the scheme for magnetite-dominated Archean IFs using samples from the hematite-poor Asbestos Hills Subgroup IF, Transvaal Supergroup, South Africa. Previously commonly-used hydroxylamine-HCl and dithionite leaches were omitted since ferric oxides are quantitatively insignificant in these IF samples. The acetate leach was tested at variable temperatures, reaction times and under different atmospheres in order to ensure that all micro-crystalline Fe-carbonates were effectively dissolved, resulting in an optimum extraction for 48h at 50°C under anoxic conditions. The dissolution of magnetite by NH4-oxalate was also tested, resulting in an optimum extraction for 24h under an ambient atmosphere. Finally, a HF-HClO4-HNO3 leach was used to dissolve the residual silicate fraction which has to date not been considered in detail in IF. Accuracy of the extraction technique was generally excellent, as verified using 1) elemental recoveries, 2) comparison of major and trace element distributions against mineralogy and 3) comparison to results from microanalytical techniques.This study focuses on the distribution of three frequently used geochemical proxies in IF; U, Mo and Cr. Molybdenum abundances in the Kuruman and Griquatown IF are low and show an apparent correlation with mineralogical variability, as determined by the sequential extraction. This suggests that changes in bulk-rock mineralogy, rather than redox chemistry might significantly affect Mo stable isotopes. For Cr, a minor bulk-rock stratigraphic increase can be related to the oxide and silicate fraction. However, a positive relationship with Zr indicates that this was also controlled by detrital or volcanic ash input. Uranium is predominantly bound to the silicate fraction and shows clear correlations with Zr and Sc implying detrital reworking under anoxic conditions. The discrepant behaviour of these three proxies indicate that mineralogy should be taken into account when interpreting heterogeneous bulk-rock samples and that fraction specific techniques will provide new insights into the evolution of atmosphere and ocean chemistry.

Influence of palaeoweathering on trace metal concentrations and environmental proxies in black shales

The mineralogical and chemical compositions of Lower Carboniferous (Tournaisian) marine black shale from the Kowala quarry, the Holy Cross Mountains, Poland, were investigated. This study focuses on disturbances in palaeoenvironmental proxies caused by palaeoweathering, which progressively changed the major and trace element abundances. Palaeomagnetic investigations reveal that the Devonian – Carboniferous succession was weathered during the Permian-Triassic by the infiltration of oxidizing fluids related to karstification following post-Variscan exhumation. The weathering process led to vermiculitization of chlorite, partial dissolution of calcite and replacement of pyrite by hematite and goethite. Moreover, the concentrations of some trace metals, including Co, Cu, Pb, Mo, Ni, As and U, significantly decreased. Consequently, some elemental abundance ratios that are used as environmental proxies, including U/Th, Ni/Co and V/Cr, were altered. Elements that are bound to iron sulphides (e.g., Mo) appear to be especially prone to mobilization by even a lightly weathered black shale. The documented weathering, including changes in elemental concentrations, can potentially create misinterpretations of the original palaeoenvironmental conditions. In addition, the palaeoweathering of the studied samples appears to have substantially changed the carbon, oxygen, nitrogen and molybdenum stable isotope values. The nitrogen and molybdenum stable isotope ratios, in particular, appear to be most sensitive to the effects of weathering and therefore are good indicators of (palaeo)weathering processes. The major cause of these changes is the decay of organic matter and pyrite. For the organic carbon stable isotopes ratios, the main factor that controlls this process appears to be the preferential degradation of labile organic matter. A combination of the total organic carbon (TOC), total sulphur (TS) content, Mo concentration and stable isotope compositions seems to be the most useful for identify (palaeo)weathering. Our results suggest that reductions in TS and Mo in tandem with diminished Mo stable isotope values in the absence of obvious changes to the TOC content provide the most compelling evidence of (palaeo)weathering.

The effects of magmatic processes and crustal recycling on the molybdenum stable isotopic composition of Mid-Ocean Ridge Basalts

Molybdenum (Mo) stable isotopes hold great potential to investigate the processes involved in planetary formation and differentiation. However their use is currently hampered by the lack of understanding of the dominant controls driving mass-dependent fractionations at high temperature. Here we investigate the role of magmatic processes and mantle source heterogeneities on the Mo isotope composition of Mid-Ocean Ridges Basalts (MORBs) using samples from two contrasting ridge segments: (1) the extremely fast spreading Pacific–Antarctic (66–41°S) section devoid of plume influence and; (2) the slow spreading Mohns–Knipovich segment (77–71°N) intercepted by the Jan Mayen Plume (71°N). We show that significant variations in Mo stable isotope composition exist in MORBs with δ98/95Mo ranging from −0.24‰ to +0.15‰ (relative to NIST SRM3134). The absence of correlation between δ98/95Mo and indices of magma differentiation or partial melting suggests a negligible impact of these processes on the isotopic variations observed. On the other hand, the δ98/95Mo variations seem to be associated with changes in radiogenic isotope signatures and rare earth element ratios (e.g., (La/Sm)N), suggesting mantle source heterogeneities as a dominant factor for the δ98/95Mo variations amongst MORBs. The heaviest Mo isotope compositions correspond to the most enriched signatures, suggesting that recycled crustal components are isotopically heavy compared to the uncontaminated depleted mantle. The uncontaminated depleted mantle shows slightly sub-chondritic δ98/95Mo, which cannot be produced by core formation and, therefore, more likely result from extensive anterior partial melting of the mantle. Consequently, the primitive δ98/95Mo composition of the depleted mantle appears overprinted by the effects of both partial melting and crustal recycling.

Nuclear spectroscopy of molybdenum isotopes

The dependence of the properties of low-lying states of Mo isotopes on the mass number A = 83–117 is studied based on the collective and shell models of atomic nuclei. The variation of the nuclear shape with an increasing number of neutrons influences strongly the properties of excited states of Mo isotopes. Decay channels of isovector giant dipole resonance with emission of protons and neutrons are studied in the framework of the combined model. The basic mechanisms of the production of stable Mo isotopes in astrophysical nuclear reactions are described.

Measurement of the 92,93,94,100Mo(γ,n) reactions by Coulomb Dissociation

The Coulomb Dissociation (CD) cross sections of the stable isotopes 92,94,100Mo and of the unstable isotope 93Mo were measured at the LAND/R3B setup at GSI Helmholtzzentrum für Schwerionenforschung in Darmstadt, Germany. Experimental data on these isotopes may help to explain the problem of the underproduction of 92,94Mo and 96,98Ru in the models of p-process nucleosynthesis. The CD cross sections obtained for the stable Mo isotopes are in good agreement with experiments performed with real photons, thus validating the method of Coulomb Dissociation. The result for the reaction 93Mo(γ,n) is especially important since the corresponding cross section has not been measured before. A preliminary integral Coulomb Dissociation cross section of the 94Mo(γ,n) reaction is presented. Further analysis will complete the experimental database for the (γ,n) production chain of the p-isotopes of molybdenum.

Integral experiment on molybdenum with DT neutrons at JAEA/FNS

An integral experiment on molybdenum is performed with a DT neutron source at JAEA/FNS. A Mo assembly is covered with lithium oxide blocks in order to reduce background neutrons inside the assembly. Several reaction rates and fission rates are measured along the central axis inside the assembly and compared with calculated ones with the Monte Carlo transport code MCNP5-1.40 and recent nuclear data libraries of ENDF/B-VII.1, JENDL-4.0, and JEFF-3.2. The calculated results generally show underestimation. From our detailed analysis, it is concluded that the (n,2n) cross section data of all the Mo stable isotopes in JEFF-3.2 are more suitable than those in JENDL-4.0 and the (n,γ) cross section data of 92Mo, 94Mo, 95Mo, 96Mo, 97Mo, and 100Mo in JENDL-4.0 are overestimated.

The stable isotope composition of vanadium, nickel, and molybdenum in crude oils

Crude oils often have high concentrations of transition metals including vanadium (V), nickel (Ni), iron (Fe), and to a lesser extent molybdenum (Mo). Determining the conditions under which these metals enter into crude oil is of interest for the understanding of biogeochemical cycles and the pathways leading to oil formation. This study presents the first high precision measurements of V, Ni, and Mo stable isotopes determined for a set of globally distributed crude oils as a first examination of the magnitude of potential stable isotope fractionation. Vanadium stable isotope compositions are presented for crude oils formed from different source rocks spanning a range of geologic ages (Paleozoic–Tertiary) and are complemented by Ni and Mo stable isotope compositions on a subset of crude oils produced from lacustrine source rocks in the Campos Basin, Brazil. The crude oils span a wide range of V and Mo isotope compositions, and display more restricted Ni stable isotope signatures. Overall, the stable isotope composition of all three systems overlaps with previously determined values for igneous and inorganic sedimentary materials. Comparisons between vanadium concentration and stable isotope composition yield distinct clusters associated with crude oils predominantly derived from terrestrial/lacustrine or marine/carbonate source rocks. The Ni stable isotope signatures of studied crude oils are similar to that of carbonaceous shales. The Mo stable isotope signatures of the lacustrine sourced crude oils are similar to what is observed for rivers. This indicates trace metal stable isotopic composition of crude oils are unlikely to result from mass dependent fractionation associated with the generation, expulsion, and migration of petroleum and are instead primarily inherited from the initial sedimentary organic matter or metal bearing fluids present during metalation. In contrast, although Mo stable isotopes also span a wide range of values, they do not appear to be correlated with source rock lithology, perhaps suggestive of a greater role for secondary processes. Finally, both V and Ni stable isotope compositions co-vary with V/(V+Ni), a commonly used parameter in determining crude oil grade. Since V/(V+Ni) ratios reflect redox conditions, the correlation implies that stable V and Ni isotope compositions may also respond to the redox conditions of the depositional environment. The contrasting behavior of these three isotope systems in this initial dataset provides fundamental guidance for future investigation to fully exploit the potential of these new isotopic tracers. These isotope tracers can be developed to determine a broad range of factors fundamental to the formation and preservation of petroleum source rocks that spans from provenance evaluation to paleoredox chemistry.

Evidence from molybdenum and iron isotopes and molybdenum–uranium covariation for sulphidic bottom waters during Eastern Mediterranean sapropel S1 formation

Redox exerts a critical control on organic carbon-rich sedimentation. This is particularly true for Eastern Mediterranean sapropels where seawater stratification is regarded as a major driving force for oxygen depletion, but in which sulphidic (euxinic) bottom waters occur only sporadically. Here we apply a powerful array of geochemical proxies (Fe and Mo stable isotopes together with Mo/U ratios and redox sensitive trace elements (RSTE)) to the determination of water redox evolution during the deposition of Holocene S1 sapropel and its underlying and overlying sediments (ODP core 967D; 2550 m depth).RSTE are asymmetrically distributed within the sapropel, with peak enrichments occurring in its lower (early) part. Negative correlations are found between δFe57 and both Fe/Al and S wt% in the lower sapropel, and are consistent with the benthic Fe shuttle model Fe enrichment in euxinic basins. MoEF/UEF enrichment factor variations show well defined trends identical to those proposed for open marine settings, in which sub-oxic conditions in the background sediments give way to sulphidic waters at the RSTE peak in the lower sapropel. The most notable features of the Mo isotope profile are ‘atypically’ light values (δMo98/95<−0.7‰) in the lower sapropel. Such light Mo isotope values (relative to sea water δMo98/95=2.3‰) have been related to oxic remobilisation. However, negative correlations between δMo98/95 and Fe/Al, Ba/Al, Mo/Al and S imply that the lowest Mo isotopic compositions are associated with peak reducing conditions. Taken in conjunction with the evidence from the other proxies for a sulphidic water column, the light Mo isotope values in the lower sapropel are best explained by a large isotopic fractionation between sea water molybdate and thiomolybdate species in mildly euxinic bottom waters ([H2S]aq <10 μM). The data from this study thus show that hitherto unrecognised euxinic conditions occur during the early stages of deposition of the Holocene sapropel S1. Molybdenum isotopes and Ba/Al ratios identify a short-lived sapropel re-ventilation event timed to coincide with the 8.2 ka cold climatic Event.

Detailed study of the neutral-current neutrino–nucleus scattering off the stable Mo isotopes

Abstract For neutrino detection and for various applications in astrophysics the knowledge of the nuclear responses to astrophysical neutrinos is crucial. Recent studies of neutrino interactions with the 100 Mo nucleus and the other stable molybdenum isotopes are important for the planned MOON (Mo Observatory of Neutrinos) detector. To this aim, in the present work we perform detailed nuclear structure calculations for the neutral-current neutrino–nucleus scattering off the stable molybdenum isotopes. We focus on the differential and total neutrino–nucleus cross sections as well as on flux averaged cross sections to various supernova neutrino spectra. We also propose a more efficient method for the computations of the corresponding nuclear matrix elements. By employing this method we extend our previous calculations for the odd isotopes ( 95 Mo and 97 Mo) where also couplings to high-lying QRPA (quasiparticle random-phase approximation) phonons are included in the quasiparticle-phonon basis. It is established in this work that the inclusion of high-lying QRPA excitations are essential for the description of the neutrino–nucleus scattering off open-shell odd-mass nuclei.