Measured Abundance Ratios Research Articles

Three-Dimensional Nonlocal Thermodynamic Equilibrium Abundance Analyses of Late-Type Stars

The chemical compositions of stars encode the history of the universe and are thus fundamental for advancing our knowledge of astrophysics and cosmology. However, measurements of elemental abundance ratios, and our interpretations of them, strongly depend on the physical assumptions that dictate the generation of synthetic stellar spectra. Three-dimensional radiation-hydrodynamic (3D RHD) box-in-a-star simulations of stellar atmospheres offer a more realistic representation of surface convection occurring in late-type stars than do traditional one-dimensional (1D) hydrostatic models. As evident from a multitude of observational tests, the coupling of 3D RHD models with line formation in nonlocal thermodynamic equilibrium (non-LTE) today provides a solid foundation for abundance analysis for many elements. This review describes the ongoing and transformational work to advance the state of the art and replace 1D LTE spectrum synthesis with its 3D non-LTE counterpart. In summary: ▪3D and non-LTE effects are intricately coupled, and consistent modeling thereof is necessary for high-precision abundances; such modeling is currently feasible for individual elements in large surveys. Mean 3D (〈3D〉) models are not adequate as substitutes.▪The solar abundance debate is presently dominated by choices and systematic uncertainties that are not specific to 3D non-LTE modeling.▪3D non-LTE abundance corrections have a profound impact on our understanding of FGK-type stars, exoplanets, and the nucleosynthetic origins of the elements.

Discovery of an Extremely r-process-enhanced Thin-disk Star with [Eu/H] = +0.78

Highly r-process-enhanced (RPE) stars are rare and usually metal poor ([Fe/H] < −1.0), and they mainly populate the Milky Way halo and dwarf galaxies. This study presents the discovery of a relatively bright (V = 12.72), highly RPE (r-II) star ([Eu/Fe] = +1.32, [Ba/Eu] = −0.95), LAMOST J020623.21+494127.9. This star was selected from the Large Sky Area Multi-Object Fiber Spectroscopic Telescope medium-resolution (R ∼ 7500) spectroscopic survey; follow-up high-resolution (R ∼ 25,000) observations were conducted with the High Optical Resolution Spectrograph installed on the Gran Telescopio Canarias. The stellar parameters (T eff = 4130 K, logg = 1.52, [Fe/H] = −0.54, ξ = 1.80 km s−1) have been inferred taking into account nonlocal thermodynamic equilibrium effects. The abundances of [Ce/Fe], [Pr/Fe], and [Nd/Fe] are +0.19, +0.65, and +0.64, respectively, relatively low compared to the Solar r-process pattern normalized to Eu. This star has a high metallicity ([Fe/H] = −0.54) compared to most other highly RPE stars and has the highest measured abundance ratio of Eu to H ([Eu/H] = +0.78). It is classified as a thin-disk star based on its kinematics and does not appear to belong to any known stream or dwarf galaxy.

Molecular isotopologue measurements toward super star clusters and the relation to their ages in NGC 253 with ALCHEMI

Context. Determining the evolution of the CNO isotopes in the interstellar medium (ISM) of starburst galaxies can yield important constraints on the ages of super star clusters (SSCs), or on other aspects and factors contributing to their evolution, such as the initial mass function (IMF). Due to the time-dependent nature of the abundances of isotopes within the ISM – as they are supplied from processes such as nucleosynthesis or chemical fractionation –, this provides the opportunity to test whether or not isotope ratios trace the ages of highly star-forming regions, such as SSCs. Aims. The goal of this study is to investigate whether the isotopic variations in SSC regions within NGC 253 are correlated with their different ages as derived from stellar population modelling. Methods. We measured abundance ratios of CO, HCN, and HCO+ isotopologues in six regions containing SSCs within NGC 253 using high-spatial-resolution (1.6″, ∼28 pc) data from the ALCHEMI (ALma Comprehensive High-resolution Extragalactic Molecular Inventory) ALMA Large program. We then analysed these ratios using RADEX radiative transfer modelling, with the parameter space sampled using the nested sampling Monte Carlo algorithm MLFriends. These abundance ratios were then compared to ages predicted in each region via the fitting of observed star-formation tracers (such as Brγ) to Starburst99 starburst stellar population evolution models. Results. We determined the isotopic column density ratios across multiple regions of SSC activity in NGC 253 using non-LTE radiative transfer modelling. We do not find any significant trend with age for the CO and HCN isotopologue ratios on timescales of the ages of the SSC* regions observed. However, HCO+ may show a correlation with age over these timescales in 12C/13C. Conclusions. The driving factors of these ratios within SSCs could be the IMF or fractionation effects. To further probe these effects in SSCs over time, a larger sample of SSCs must be observed spanning a larger age range.

The complex stellar system M 22: constraining the chemical enrichment from AGB stars using magnesium isotope ratios

ABSTRACT The complex star cluster M 22 (NGC 6656) provides a unique opportunity for studying the slow neutron capture (s-)process nucleosynthesis at low metallicity due to its two stellar groups with distinct iron-peak and neutron capture element abundances. Previous studies attribute these abundance differences to pollution from $3-6 \ \rm {M}_{\odot }$ asymptotic giant branch (AGB) stars which produce significant quantities of the neutron-rich Mg isotopes 25Mg and 26Mg. We report the first-ever measurements of Mg isotopic abundance ratios at $\rm {[Fe/H]} \ \sim -2$ in a globular cluster-like system using very high-resolution and signal-to-noise spectra (R = 110 000, S/N = 300 per pixel at 514 nm) from the VLT/UVES spectrograph for six stars; three in each s-process group. Despite the presence of star-to-star variations in 24Mg, 25Mg, and 26Mg, we find no correlation with heavy element abundances, implying that the nucleosynthetic source of s-process enrichment must not influence Mg isotope ratios. Instead, a key result of this work is that we identify correlations between 26Mg/24Mg and some light elements. Using a custom suite of AGB nucleosynthesis yields tailored to the metallicity of M 22, we find that low mass ($\sim 1 \rm {-} 3 \ \rm {M}_{\odot }$) AGB stars are capable of reproducing the observed s-process abundances of M 22 and that the absence of any difference in Mg isotope ratios between the two s-process groups precludes AGBs with masses above $\sim 3 \ \rm {M}_{\odot }$. This places tighter constraints on possible formation scenarios and suggests an age difference of at least $\sim 280 \rm {-} 480 \ \rm {Myr}$ between the two populations which is independent of isochrone fitting.

Stellar Population Astrophysics (SPA) with the TNG

Context. Exploring the Galactic chemical evolution and enrichment scenarios with open clusters (OCs) allows us to understand the history of the Milky Way disk. High-resolution spectra of OCs are a crucial tool, as they provide precise chemical information, to combine with precise distances and ages. Aims. The aim of the Stellar Population Astrophysics (SPA) project is to derive homogeneous and accurate comprehensive chemical characterization of a number of poorly studied OCs. Methods. Using the HARPS-N echelle spectrograph at the Telescopio Nazionale Galileo (TNG), we obtained high-resolution spectra of giant stars in 18 OCs, 16 of which are chemically characterized for the first time, and two of which are well studied for comparison. The OCs in this sample have ages from a few tens of Myr to 4 Gyr, with a prevalence of young clusters. We already presented the radial velocities and atmospheric parameters for them in a previous SPA paper. Here, we present results for the α-elements O, Mg, Si, Ca and Ti, and the light elements Na and Al, all determined by the equivalent width method. We also measured Li abundance through the synthesis method. Results. We discuss the behaviors of lithium, sodium and aluminum in the context of stellar evolution. For Na and Al, we compare our findings with models to investigate their behaviors as a function of mass, suggesting that Na mixing to the surface might start in masses as low as 2 M⊙. We study the radial, vertical, and age trends for the measured abundance ratios in a sample that combines our results and recent literature for OCs, finding significant (positive) gradients only for [Mg/Fe] and [Ca/Fe] in all cases. Finally, we compare O and Mg in the combined sample with chemo-dynamical models, finding a good agreement for intermediate-age and old clusters. There is a sharp increase in the abundance ratios measured among very young clusters (age &lt; 300 Myr), accompanied by a poorer fit with the models for O and Mg, likely related to the inadequacy of traditional model atmospheres and methods in the derivation of atmospheric parameters and abundance ratios for stars of such young ages.

Chemical Abundances of Young Massive Clusters in NGC 1313∗ ∗ Based on observations made with ESO telescopes at the La Silla Paranal Observatory under program ID 084.B-0468(A).

We analyze spectroscopic observations of five young massive clusters (YMCs) in the barred spiral galaxy NGC 1313 to obtain detailed abundances from their integrated light. Our sample of YMCs was observed with the X-shooter spectrograph on the Very Large Telescope. We make use of theoretical isochrones to generate synthetic integrated-light spectra, iterating on the individual elemental abundances until converging on the best fit to the observations. We measure abundance ratios for [Ca/Fe], [Ti/Fe], [Mg/Fe], [Cr/Fe], and [Ni/Fe]. We estimate an Fe abundance gradient of −0.124 ± 0.034 dex kpc−1, and a slightly shallower α gradient of −0.093 ± 0.009 dex kpc−1. This is in contrast to previous metallicity studies that focused on the gas-phase abundances, which have found NGC 1313 to be the highest-mass barred galaxy known not to have a radial abundance gradient. We propose that the gradient discrepancy between the different studies originates from the metallicity calibrations used to study the gas-phase abundances. We also observe an age–metallicity trend that supports a scenario of constant star formation throughout the galaxy, with a possible burst in star formation in the southwest region where YMC NGC 1313–379 is located.

Spatially Resolved X-Ray Study of Supernova Remnant G306.3–0.9 with Unusually High Calcium Abundance

Abstract G306.3–0.9 is an asymmetric Galactic supernova remnant (SNR), whose progenitor has been thought to be a Type Ia supernova (SN), but its high Ca abundance appears inconsistent with the Type Ia origin. Hoping to uncover the reason for its asymmetry and the origin of this SNR, we performed a spatially resolved X-ray spectroscopic analysis of XMM-Newton and Chandra observation data. We divided the SNR into 13 regions and analyzed the spectra using two-temperature models (0.2 keV + 1 keV). Compared to the southwestern regions, the northeastern regions have higher metal abundances and a lower gas density. This suggests that the asymmetric morphology results from the nonuniform ambient environment. We found that neither Type Ia nor core-collapse SN models can account for the abnormally high abundance ratios of Ar/Si, Ca/Si, or the shape of the abundance curve. A comparison with the Ca-rich transient models suggests that G306.3–0.9 is likely to be the first identified Galactic Ca-rich transient remnant, although the theoretical production of element S is lower. We also note that the conclusion for the SNR’s origin relies on the measured abundance ratios and existing nucleosynthesis models. Between two groups of Ca-rich transient explosion models, we prefer the He shell detonation for an accreting white dwarf, rather than the merger of a white dwarf and a neutron star.

The relative supernovae contribution to the chemical enrichment history of Abell 1837

ABSTRACT In this paper, we report the relative supernovae (SNe) contribution to the metal budget of the intracluster medium (ICM) of the Abell 1837 galaxy cluster at redshift z = 0.069. For this purpose, we analysed the hot ICM of the cluster and obtained radial metal distributions using XMM–Newton archival data with a total exposure of ∼100 ks. These metal measurements consist of Mg, Si, S, Fe and Ni within a radius of 0.7 R500, which is divided into three concentric annuli. In order to explain the observed metal abundance pattern in terms of relative supernova contributions, we used our newly developed code SNeRatio, which utilizes theoretical nucleosynthesis models. This study covers the most recent 3D Type Ia SN and core-collapse SN yield tables. All combinations of these theoretical yields were fitted with our measured abundance ratios, and statistically acceptable ones were selected. Each of these models was found to predict a uniform SNIa percentage contribution to the total SNe from the cluster centre to the outskirts and to form an SNIa ratio distribution with a mean of 39 ± 14${{\ \rm per\ cent}}$. This uniformity is consistent with the early enrichment scenario, which assumes that metal production processes begin in the early phase of cluster formation, namely the proto-cluster phase at epoch z ≥ 2.

The low-luminosity Type II SN 2016aqf: a well-monitored spectral evolution of the Ni/Fe abundance ratio

ABSTRACTLow-luminosity Type II supernovae (LL SNe II) make up the low explosion energy end of core-collapse SNe, but their study and physical understanding remain limited. We present SN 2016aqf, an LL SN II with extensive spectral and photometric coverage. We measure a V-band peak magnitude of −14.58 mag, a plateau duration of ∼100 d, and an inferred 56Ni mass of 0.008 ± 0.002 M⊙. The peak bolometric luminosity, Lbol ≈ 1041.4 erg s−1, and its spectral evolution are typical of other SNe in the class. Using our late-time spectra, we measure the [O i] λλ6300, 6364 lines, which we compare against SN II spectral synthesis models to constrain the progenitor zero-age main-sequence mass. We find this to be 12 ± 3 M⊙. Our extensive late-time spectral coverage of the [Fe ii] λ7155 and [Ni ii] λ7378 lines permits a measurement of the Ni/Fe abundance ratio, a parameter sensitive to the inner progenitor structure and explosion mechanism dynamics. We measure a constant abundance ratio evolution of $0.081^{+0.009}_{-0.010}$ and argue that the best epochs to measure the ratio are at ∼200–300 d after explosion. We place this measurement in the context of a large sample of SNe II and compare against various physical, light-curve, and spectral parameters, in search of trends that might allow indirect ways of constraining this ratio. We do not find correlations predicted by theoretical models; however, this may be the result of the exact choice of parameters and explosion mechanism in the models, the simplicity of them, and/or primordial contamination in the measured abundance ratio.

Nonequilibrium Ionization Effects on Coronal Plasma Diagnostics and Elemental Abundance Measurements

Abstract Plasma diagnostics and elemental abundance measurements are crucial to help us understand the formation and dynamics of the solar wind. Here we use a theoretical solar wind model to study the effect of nonequilibrium ionization (NEI) on plasma diagnostic techniques applied to line intensities emitted by the fast solar wind. We find that NEI almost always changes the spectral line intensities with up to 120% difference for the lighter elements and for higher charge states of Fe even below 1.5 solar radii (R s ). The measured plasma density, temperature, and differential emission measure are only slightly affected by NEI. However, NEI significantly affects the first-ionization potential (FIP) bias and abundance ratio measurements, producing an error of up to a factor 4 at 1.5 R s for the Mg-to-Ne, Fe-to-S, and Ar-to-Fe ratios when EI is assumed. We conclude that it is very important to consider the NEI effect when spectral line intensities are synthesized and the FIP bias and elemental abundance are measured.

Limits on stable iron in Type Ia supernovae from near-infrared spectroscopy

We obtained optical and near infrared spectra of Type Ia supernovae (SNe Ia) at epochs ranging from 224 to 496 days after the explosion. The spectra show emission lines from forbidden transitions of singly ionised iron and cobalt atoms. We used non-local thermodynamic equilibrium (NLTE) modelling of the first and second ionisation stages of iron, nickel, and cobalt to fit the spectra using a sampling algorithm allowing us to probe a broad parameter space. We derive velocity shifts, line widths, and abundance ratios for iron and cobalt. The measured line widths and velocity shifts of the singly ionised ions suggest a shared emitting region. Our data are fully compatible with radioactive 56Ni decay as the origin for cobalt and iron. We compare the measured abundance ratios of iron and cobalt to theoretical predictions of various SN Ia explosion models. These models include, in addition to 56Ni, different amounts of 57Ni and stable 54,56Fe. We can exclude models that produced only 54,56Fe or only 57Ni in addition to 56Ni. If we consider a model that has 56Ni, 57Ni, and 54,56Fe then our data imply that these ratios are 54,56Fe / 56Ni = 0.272 ± 0.086 and 57Ni / 56Ni = 0.032 ± 0.011.

Direct, Precise Measurements of Isotopologue Abundance Ratios in CO2 Using Molecular Absorption Spectroscopy: Application to Δ17O.

We present an ultrasensitive absorption spectrometer based on a 30 Hz/s stability, sub-kHz line width laser source coupled to a high-stability cavity-ring-down-spectroscopy setup. It provides direct and precise measurements of the isotopic ratios δ17O and δ18O in CO2. We demonstrate the first optical absorption measurements of 17O anomalies in CO2 with a precision better than 10 ppm, matching the requirements for paleo-environmental applications. This illustrates how optical absorption methods have become a competitive alternative to state-of-the-art isotopic ratio mass spectrometry techniques.

Argon isotopes as tracers for martian atmospheric loss

Recent measurements of the present-day Ar abundance and isotopic ratios in the martian atmosphere by the SAM instrument suite onboard the Curiosity rover can be used to constrain the atmospheric and volatile evolution. We have examined the role of volcanic outgassing, escape to space via sputtering, crustal erosion, impact delivery, and impact erosion in reproducing the Ar isotope ratios from an initial state 4.4 billion years ago. To investigate the effects of each of these processes, their timing, and their intensity we have modeled exchanges of Ar isotopes between various reservoirs (mantle, crust, atmosphere, etc.) throughout Mars’ history. Furthermore, we use present-day atmospheric measurements to determine the parameter space consistent with observations. We find that significant loss to space (at least 48% of atmospheric 36Ar) is required to match the observed 36Ar/38Ar ratio. Our estimates of volcanic outgassing do not supply sufficient 40Ar to the atmosphere to match observations, so in our model at least 31% of 40Ar produced in the crust must have also been released to the atmosphere. Of the total 40Ar introduced into the atmosphere about 25% must have been lost to space. By adding the present-day isotopic abundances with our results of total integrated Ar loss we find a “restored” value of atmospheric 40Ar/36Ar, which represents what that ratio would be if the total integrated Ar loss had remained in the atmosphere. We determine the restored value to be ∼900–1500. This is below the present martian atmospheric value (1900 ± 300), but 3–5 times greater than the terrestrial value.

Ca ii absorbers in the Sloan Digital Sky Survey: element abundances and dust

We present measurements of element abundance ratios and dust in Ca ii absorbers identified in Sloan Digital Sky Survey DR7+DR9. In an earlier paper we formed a statistical sample of 435 Ca ii absorbers and postulated that their statistical properties might be representative of at least two populations of absorbers. Here, we show that if the absorbers are roughly divided into two subsamples with Ca ii rest equivalent widths larger and smaller than |$W_0^{\lambda 3934} = 0.7$| Å, they are then representative of two physically different populations. Comparisons of abundance ratios between the two Ca ii absorber populations indicate that the weaker |$W_0^{\lambda 3934}$| absorbers have properties consistent with halo-type gas, while the stronger absorbers have properties intermediate between halo- and disc-type gas. We also show that, on average, the dust-extinction properties of the overall sample is consistent with a Large Magellanic Cloud or Small Magellanic Cloud dust law, and the stronger absorbers are nearly six times more reddened than their weaker counterparts. The absorbed-to-unabsorbed composite flux ratio at λrest = 2200 Å is |$\mathcal {R} \approx 0.73$| and E(B − V) ≈ 0.046 for the stronger Ca ii absorbers (⁠|$W_0^{\lambda 3934} \ge 0.7$| Å), and |$\mathcal {R} \approx 0.95$| and E(B − V) ≈ 0.011 for the weaker Ca ii absorbers (⁠|$W_0^{\lambda 3934} < 0.7$| Å).

The mass–metallicity relation of tidal dwarf galaxies

Dwarf galaxies generally follow a mass-metallicity (MZ) relation, where more massive objects retain a larger fraction of heavy elements. Young tidal dwarf galaxies (TDGs), born in the tidal tails produced by interacting gas-rich galaxies, have been thought to not follow the MZ relation, because they inherit the metallicity of the more massive parent galaxies. We present chemical evolution models to investigate if TDGs that formed at very high redshifts, where the metallicity of their parent galaxy was very low, can produce the observed MZ relation. Assuming that galaxy interactions were more frequent in the denser high-redshift universe, TDGs could constitute an important contribution to the dwarf galaxy population. The survey of chemical evolution models of TDGs presented here captures for the first time an initial mass function (IMF) of stars that is dependent on both the star formation rate and the gas metallicity via the integrated galactic IMF (IGIMF) theory. As TDGs form in the tidal debris of interacting galaxies, the pre-enrichment of the gas, an underlying pre-existing stellar population, infall, and mass dependent outflows are considered. The models of young TDGs that are created in strongly pre-enriched tidal arms with a pre-existing stellar population can explain the measured abundance ratios of observed TDGs. The same chemical evolution models for TDGs, that form out of gas with initially very low metallicity, naturally build up the observed MZ relation. The modelled chemical composition of ancient TDGs is therefore consistent with the observed MZ relation of satellite galaxies.

HERSCHEL FINDS EVIDENCE FOR STELLAR WIND PARTICLES IN A PROTOSTELLAR ENVELOPE: IS THIS WHAT HAPPENED TO THE YOUNG SUN?

There is evidence that the young Sun emitted a high flux of energetic (⩾10 MeV) particles. The collisions of these particles with the material at the inner edge of the Protosolar Nebula disk induced spallation reactions that formed short-lived radionuclei, like 10Be, whose trace is now visible in some meteorites. However, it is poorly known exactly when this happened, and whether and how it affected the solar system. Here, we present indirect evidence for an ejection of energetic particles in the young protostar, OMC-2 FIR 4, similar to that experienced by the young solar system. In this case, the energetic particles collide with the material in the protostellar envelope, enhancing the abundance of two molecular ions, HCO+ and N2H+, whose presence is detected via Herschel observations. The flux of energetic particles at a distance of 1 AU from the emitting source, estimated from the measured abundance ratio of HCO+ and N2H+, can easily account for the irradiation required by meteoritic observations. These new observations demonstrate that the ejection of ⩾10 MeV particles is a phenomenon occurring very early in the life of a protostar, before the disappearance of the envelope from which the future star accretes. The whole envelope is affected by the event, which sets constraints on the magnetic field geometry in the source and opens up the possibility that the spallation reactions are not limited to the inner edge of the Protosolar Nebula disk.

Certified reference materials and reference methods for nuclear safeguards and security

Confidence in comparability and reliability of measurement results in nuclear material and environmental sample analysis are established via certified reference materials (CRMs), reference measurements, and inter-laboratory comparisons (ILCs). Increased needs for quality control tools in proliferation resistance, environmental sample analysis, development of measurement capabilities over the years and progress in modern analytical techniques are the main reasons for the development of new reference materials and reference methods for nuclear safeguards and security.The Institute for Reference Materials and Measurements (IRMM) prepares and certifices large quantities of the so-called “large-sized dried” (LSD) spikes for accurate measurement of the uranium and plutonium content in dissolved nuclear fuel solutions by isotope dilution mass spectrometry (IDMS) and also develops particle reference materials applied for the detection of nuclear signatures in environmental samples. IRMM is currently replacing some of its exhausted stocks of CRMs with new ones whose specifications are up-to-date and tailored for the demands of modern analytical techniques. Some of the existing materials will be re-measured to improve the uncertainties associated with their certified values, and to enable laboratories to reduce their combined measurement uncertainty.Safeguards involve the quantitative verification by independent measurements so that no nuclear material is diverted from its intended peaceful use. Safeguards authorities pay particular attention to plutonium and the uranium isotope 235U, indicating the so-called ‘enrichment’, in nuclear material and in environmental samples. In addition to the verification of the major ratios, n(235U)/n(238U) and n(240Pu)/n(239Pu), the minor ratios of the less abundant uranium and plutonium isotopes contain valuable information about the origin and the ‘history’ of material used for commercial or possibly clandestine purposes, and have therefore reached high level of attention for safeguards authorities. Furthermore, IRMM initiated and coordinated the development of a Modified Total Evaporation (MTE) technique for accurate abundance ratio measurements of the "minor" isotope-amount ratios of uranium and plutonium in nuclear material and, in combination with a multi-dynamic measurement technique and filament carburization, in environmental samples.Currently IRMM is engaged in a study on the development of plutonium reference materials for “age dating”, i.e. determination of the time elapsed since the last separation of plutonium from its daughter nuclides. The decay of a radioactive parent isotope and the build-up of a corresponding amount of daughter nuclide serve as chronometer to calculate the age of a nuclear material. There are no such certified reference materials available yet.

Total evaporation method for uranium isotope-amount ratio measurements

Total evaporation (TE) is an analysis technique for the measurement of uranium isotopic abundance ratios using thermal ionization mass spectrometry (TIMS). A small mass dependent bias observed in this analytical technique is determined by an external correction factor using well characterized standards (most often certified reference materials, CRMs). The technique had been demonstrated to be highly precise and accurate for major isotope-amount ratio measurements of uranium and plutonium. We compare the performance of the TE analytical technique for uranium isotope ratio measurements on two TIMS instruments (TRITON and MAT261) using well characterized CRMs from NBL and investigate the dependence of the instrumental mass bias on the amount of sample analyzed. It is concluded that the mass bias during a TIMS uranium isotopic analysis by TE is independent of the amount of material analyzed. Unlike the major ratio, minor isotope ratio measurements by TE are biased high due to peak-tailing from the major isotopes. The biases in the minor isotope ratio data using TE are evaluated using well characterized NBL CRMs.

A high-throughput method for the determination of Os concentrations and isotope ratio measurements in small-size biological samples

An analytical method allowing multi-element characterization by external calibration, osmium (Os) concentration determination by isotope dilution (ID) and 187Os/188Os isotope abundance ratio measurement from a single sample preparation was developed. The method consists of microwave-assisted, closed-vessel acid digestion of small (0.01–0.4 g dry weight) biological samples spiked with Os solution enriched in a 190Os isotope followed by concentration and Os isotope ratio measurements using double-focusing, sector field inductively coupled plasma mass-spectrometry (ICP-SFMS) operated with methane addition to the plasma and solution nebulization (SN) sample introduction. For samples with Os content below 500 pg, complementary analysis using gas-phase introduction (GPI) on the remaining sample digests was performed. The use of disposable plastic lab ware for sample digestion and analysis by SN ICP-SFMS circumvents Os carry-over effects and improves the sample throughput and cost-efficiency of the method. For a 0.1 g dried sample, Os method limits of detection (MLODs) of 2 pg g−1 and 0.2 pg g−1 were obtained using SN or GPI, respectively. Long-term reproducibility of 187Os/188Os isotope abundance ratio measurements using the GPI approach was better than 1.5% RSD for our in-house control sample (moose kidney) with an Os concentration of approximately 5 pg g−1. Os data for several commercially available reference materials of biological or plant origin (not certified for Os) are presented. The method was used in the large scale bio-monitoring of free-living bank voles from an area affected by anthropogenic Os emissions.

Isotopic analyses by ICP-MS in clinical samples

This critical review focuses on inductively coupled plasma mass spectrometry (ICP-MS) based applications for isotope abundance ratio measurements in various clinical samples relevant to monitoring occupational or environmental exposure, human provenancing and reconstruction of migration pathways as well as metabolic research. It starts with a brief overview of recent advances in ICP-MS instrumentation, followed by selected examples that cover the fields of accurate analyte quantification using isotope dilution, tracer studies in nutrition and toxicology, and areas relying upon natural or man-made variations in isotope abundance ratios (Pb, Sr, actinides and stable heavy elements). Finally, some suggestions on future developments in the field are provided.