Mass-dependent Isotope Effect Research Articles

COSMO: Double spike optimization for sample-limited analyses of isotopically anomalous materials

The double spike (DS) technique is the gold standard by which high-precision and high-accuracy mass-dependent isotope fractionations are quantified, and has played a critical role in the recent development of numerous non-traditional stable isotope systems. The democratization of the technique is in great part due to the availability of the so-called ‘DS toolbox’, a software suite that allows for the straightforward identification of optimal DS compositions. As new applications for DS measurements arise, some additional considerations must be taken into account in deciding on an optimal double spike. In particular, sample-limited investigations of combined mass-dependent and independent isotope effects (e.g., in Early Solar System materials) present an additional challenge in determining optimal spikes.Here, we describe the cosmo software package, which specifically addresses this upcoming need in cosmochemistry/isotope geochemistry to optimize DS measurements for small samples with mass-independent anomalies (e.g., nucleosynthetic anomalies, radiogenic ingrowth). These measurements are subject to additional errors from a complementary unspiked measurement, which is necessary to properly quantify mass-dependent isotope effects during the DS inversion. The software package addresses this additional complication by offering users the ability to (i) specify additional parameters relevant to practical sample-limited analyses (e.g., instrumental transmission efficiency, number of cycles of analyses), (ii) optimize how a sample is split between unspiked and spiked measurements, and (iii) identify the internal normalization scheme that leads to the lowest uncertainty on the mass-dependent fractionation factor, α, and/or the isotope anomalies, ε. These additional functionalities were designed to operate within the DS toolbox framework and expands its applicability to a wider array of samples (i.e., extraterrestrial samples) and measurement scenarios to push the limits of new and improved instrumentation.

Magnesium magnetic isotope effects in microbiology.

Two main properties of atomic nuclei-mass and nuclear magnetic moments-are origin of many biological effects. Mass-dependent isotope effects have been studied for a long time. The effect of magnetic isotopes having a magnetic moment and spin was first shown in the early twenty-first century for the magnetic isotope magnesium 25Mg on enzymatic ATP synthesis. This stimulated the search for experimental evidence and theoretical justification of magnetic nuclei influence on biological processes. This review contains the results of scientific research on the magnesium magnetic isotope effects in microbiology. Microorganisms have been found to be sensitive to the presence of nuclear magnetic moment of magnesium isotope 25Mg compared with non-magnetic 24,26Mg isotopes.

High-precision measurement and standard calibration of triple oxygen isotopic compositions (δ18O, Δ′17O) of sulfate by F2 laser fluorination

A new approach for measuring the triple oxygen isotope composition of sulfate minerals was developed using fluorine gas and an infrared laser to generate O2. A correction for the mass-dependent isotope effect observed during barite fluorination was rigorously calibrated. Analyte gas purification was performed via numerous cryofocus steps and the introduction of an in-line gas chromatograph. As with previous methods, our fluorination technique still requires pairing with independent δ18O measurements made by TC/EA conversion to carbon monoxide, but leads to higher yields than BrF5-based methods. We first calibrated our method against known silicate standards (UWG-2, SCO, NBS-28). Following from this, we report high-precision triple oxygen isotope ratios for international sulfate standards (IAEA-SO-5, IAEA-S O-6, NBS-127), and an internal laboratory standard, JMG. Replicate analyses of JMG yielded a Δ′17O value of −0.057 ± 0.004‰ (standard error), demonstrating per-meg level precision that approaches instrumental limits. We provide δ17O and δ18O values that can be translated into any preferred reference frame for comparison with gases, water, or rocks/minerals. Quantification of differences in triple oxygen isotope composition of the standard reference materials further enables application of this measure and approach on environmental and geological materials.

Unexpected variations in the triple oxygen isotope composition of stratospheric carbon dioxide

We report observations of stratospheric CO2 that reveal surprisingly large anomalous enrichments in (17)O that vary systematically with latitude, altitude, and season. The triple isotope slopes reached 1.95 ± 0.05(1σ) in the middle stratosphere and 2.22 ± 0.07 in the Arctic vortex versus 1.71 ± 0.03 from previous observations and a remarkable factor of 4 larger than the mass-dependent value of 0.52. Kinetics modeling of laboratory measurements of photochemical ozone-CO2 isotope exchange demonstrates that non-mass-dependent isotope effects in ozone formation alone quantitatively account for the (17)O anomaly in CO2 in the laboratory, resolving long-standing discrepancies between models and laboratory measurements. Model sensitivities to hypothetical mass-dependent isotope effects in reactions involving O3, O((1)D), or CO2 and to an empirically derived temperature dependence of the anomalous kinetic isotope effects in ozone formation then provide a conceptual framework for understanding the differences in the isotopic composition and the triple isotope slopes between the laboratory and the stratosphere and between different regions of the stratosphere. This understanding in turn provides a firmer foundation for the diverse biogeochemical and paleoclimate applications of (17)O anomalies in tropospheric CO2, O2, mineral sulfates, and fossil bones and teeth, which all derive from stratospheric CO2.

Mass-Independent Isotope Effects

Three fundamental properties of atomic nuclei-mass, spin (and related magnetic moment), and volume-are the source of isotope effects. The mostly deserved and popular, with almost hundred-year history, is the mass-dependent isotope effect. The first mass-independent isotope effect which chemically discriminates isotopes by their nuclear spins and nuclear magnetic moments rather than by their masses was detected in 1976. It was named as the magnetic isotope effect because it is controlled by magnetic interaction, i.e., electron-nuclear hyperfine coupling in the paramagnetic species, the reaction intermediates. The effect follows from the universal physical property of chemical reactions to conserve angular momentum (spin) of electrons and nuclei. It is now detected for oxygen, silicon, sulfur, germanium, tin, mercury, magnesium, calcium, zinc, and uranium in a great variety of chemical and biochemical reactions including those of medical and ecological importance. Another mass-independent isotope effect was detected in 1983 as a deviation of isotopic distribution in reaction products from that which would be expected from the mass-dependent isotope effect. On the physical basis, it is in fact a mass-dependent effect, but it surprisingly results in isotope fractionation which is incompatible with that predicted by traditional mass-dependent effects. It is supposed to be a function of dynamic parameters of reaction and energy relaxation in excited states of products. The third, nuclear volume mass-independent isotope effect is detected in the high-resolution atomic and molecular spectra and in the extraction processes, but there are no unambiguous indications of its importance as an isotope fractionation factor in chemical reactions.

Nuclear field shift effect of lead in ligand exchange reaction using a crown ether

Abstract Lead isotopes were fractionated by the liquid-liquid extraction technique between an aqueous phase and a crown ether. After purification by ion-exchange chemistry, the 207Pb/206Pb and 208Pb/206Pb isotopic ratios were measured by multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). Isotope fractionations > 0.05‰ have been found. The conventional equilibrium mass-dependent isotope effect estimated by an ab initio calculation was smaller than the Pb isotope fractionation experimentally obtained. Conventional mass-dependent isotope fractionation is not a valuable explanation for our results. The nuclear field shift effect, which results from the isotopic change in the nuclear size and shape, was also estimated by an ab initio method combined with a finite nucleus model. The nuclear field shift effect calculated was in agreement with our experimental results. Therefore, this study reports the first nuclear field shift effect of Pb in an equilibrium ligand exchange reaction.

Towards quantum mechanical description of the unconventional mass-dependent isotope effect in ozone: Resonance recombination in the strong collision approximation

The dependence of ozone recombination rate on the masses of oxygen isotopes is examined in the strong collision approximation by means of quantum mechanical calculations of resonance spectra of several rotating isotopomers. The measured DeltaZPE effect and its temperature dependence can be reconstructed from partial widths of narrow nonoverlapping resonances. The effect is attributed to substantial contributions of highly rotationally excited states to recombination.

Mass-Dependent and Mass-Independent Isotope Effects of Zinc in a Redox Reaction

We report the isotope fractionation of zinc (Zn) associated with a redox reaction between Zn(0) and Zn(II). Zn isotopes were found fractionated in pyrometallurgical biphase extraction between liquid zinc and molten chloride. The isotopic composition of Zn in the molten chloride phase was analyzed by multiple collector inductively coupled plasma mass spectrometry and reported as (m)Zn/64Zn (m = 66, 67, and 68) ratios. The observed isotope fractionation consists of the mass-dependent and mass-independent isotope effects. The contributions of the nuclear mass and the nuclear volume to the overall isotope effect were evaluated by employing first-principles quantum calculations and using reported isotope shifts in atomic spectra. The magnitude of the mass-dependent isotope effect was explained by the sum of the isotope effect via intramolecular vibrations and the correction to the Born-Oppenheimer electronic energy. The mass-independent isotope effect was correlated with the Gibbs free energy change in the redox reaction.

Magnetic Isotope Effect in the Photolysis of Organotin Compounds

Photolysis of organotin molecules RSnMe3 is shown to be a spin selective radical reaction accompanied by fractionation of magnetic, (117,119)Sn, and nonmagnetic, (118,120)Sn, isotopes between starting reagents and products. A primary photolysis process is a homolytic cleavage of the C-Sn bond and generation of a triplet radical pair as a spin-selective nanoreactor. Nuclear spin dependent triplet-singlet conversion of the pair results in the tin isotope fractionation. Experimentally detected isotope distribution unambiguously demonstrates that the classical, mass-dependent isotope effect is negligible in comparison with magnetic, spin-dependent isotope effect.

The magnetic isotope effect and oxygen isotope selection in chain processes of polymer oxidation

Experimental evidence based on the dependence of molecular oxygen isotope enrichment on the oxygen conversion, temperature and kinetic chain length indicate that, in chain processes of polymer oxidation, the elementary, reactions (recombination or disproportionation) of peroxy radicals are responsible for the selection of both 17O and 18O isotopes. The 17O selection is induced by a magnetic isotope effect and is sensitive to the molecular dynamics, while 18O selection is due to a classical mass-dependent isotope effect and is much less effective.