Relative Isotopic Abundances Research Articles

Krypton-85 chronometry of spent nuclear fuel

Abstract. We describe the use of the radionuclide 85Kr, which is produced by nuclear fission and has a half-life of 10.76 years, to determine the age of spent nuclear fuel. The method is based on mass-spectrometric measurement of the relative abundance of fissiogenic Kr isotopes extracted from a fuel sample, and we show that it can be applied to micron-scale particles of spent fuel that are analogous to particles that have been released into the environment from various nuclear facilities in the past. 85Kr chronometry is potentially valuable for identifying and attributing nuclear materials, grouping samples into collections of common origin that can be used to reconstruct the origin and irradiation history of the material, and verifying declared nuclear activities in the context of international monitoring programs.

Numbers of Exchangeable Hydrogens from LC-MS Data of Heavy Water Metabolically Labeled Samples.

Labeling with deuterium oxide (D2O) has emerged as one of the preferred approaches for measuring the synthesis of individual proteins in vivo. In these experiments, the synthesis rates of proteins are determined by modeling mass shifts in peptides during the labeling period. This modeling depends on a theoretical maximum enrichment determined by the number of labeling sites (NEH) of each amino acid in the peptide sequence. Currently, NEH is determined from one set of published values. However, it has been demonstrated that NEH can differ between species and potentially tissues. The goal of this work was to determine the number of NEH for each amino acid within a given experiment to capture the conditions unique to that experiment. We used four methods to compute the NEH values. To test these approaches, we used two publicly available data sets. In a de novo approach, we compute NEH values and the label enrichment from the abundances of three mass isotopomers. The other three methods use the complete isotope profiles and body water enrichment in deuterium as an input parameter. They determine the NEH values by (1) minimizing the residual sum of squares, (2) from the mole percent excess of labeling, and (3) the time course profile of the depletion of the relative isotope abundance of monoisotope. In the test samples, the method using residual sum of squares performed the best. The methods are implemented in a tool for determining the NEH for each amino acid within a given experiment to use in the determination of protein synthesis rates using D2O.

Reaching environmental levels of 244Pu by accelerator mass spectrometry at the Centro Nacional de Aceleradores

244Pu (T1/2 = 81 My) is the longest-lived, most minor, and the most understudied Pu isotope. The anthropogenic production of 244Pu is linked to nuclear detonations. Reported 244Pu/239Pu atom ratios in environmental samples range from below 10−6 to above 10−3. This work discusses the performance of the 1 MV Accelerator Mass Spectrometry system at the Centro Nacional de Aceleradores (CNA, Seville, Spain) to analyse 244Pu at environmental levels. The presence of 232Th traces in the Pu sample limits the sensitivity of the technique through the formation of the diatomic trication (232Th12C)3+, of mass 244 u, which must be suppressed by adjusting the stripper gas pressure. A244Pu background of 0.0075 fg (2 × 104 at) is demonstrated for samples that have undergone a chemical treatment. The reliability of the technique is proved through the analysis of three reference sediments provided by the International Atomic Energy Agency (IAEA-412, IAEA-465, IAEA-385). 244Pu results are complemented with 239Pu, 240Pu, 241Pu and 236U and their relative isotopic abundances are discussed.

Systemic long-distance sulfur transport and its role in symbiotic root nodule protein turnover

Sulfur is an essential nutrient for all plants, but also crucial for the nitrogen fixing symbiosis between legumes and rhizobia. Sulfur limitation can hamper nodule development and functioning. Until now, it remained unclear whether sulfate uptake into nodules is local or mainly systemic via the roots, and if long-distance transport from shoots to roots and into nodules occurs. Therefore, this work investigates the systemic regulation of sulfur transportation in the model legume Lotus japonicus by applying stable isotope labeling to a split-root system. Metabolite and protein extraction together with mass spectrometry analyses were conducted to determine the plants molecular phenotype and relative isotope protein abundances. Data show that treatments of varying sulfate concentrations including the absence of sulfate on one side of a nodulated root was not affecting nodule development as long as the other side of the root system was provided with sufficient sulfate. Concentrations of shoot metabolites did not indicate a significant stress response caused by a lack of sulfur. Further, we did not observe any quantitative changes in proteins involved in biological nitrogen fixation in response to the different sulfate treatments. Relative isotope abundance of 34S confirmed a long-distance transport of sulfur from one side of the roots to the other side and into the nodules. Altogether, these results provide evidence for a systemic long-distance transport of sulfur via the upper part of the plant to the nodules suggesting a demand driven sulfur distribution for the maintenance of symbiotic N-fixation.

Discoverer and Methodologist

During the mid–twentieth century, geochemistry—one of the core Earth sciences—underwent a spectacular transformation as a result of the introduction of electronic instruments based on physical principles. In this process, mass spectrometry became the workhorse analytical technique in isotope geochemistry. This essay concerns the dynamic relationship between discoveries of isotope systems and the variations in their relative abundances, on the one hand—discoveries that became the foundation of isotope geology—and the development of mass spectrometry, on the other. This relationship is illustrated by the career of physicist and instrument-builder Alfred O.C. Nier, who was based at the University of Minnesota in Minneapolis. Nier’s 60o-sector mass spectrometer design of 1940 endowed the instrument with powerful new capabilities, as well as facilitated its adoption outside the nuclear physics community. In the course of developing and applying the instrument, Nier also made important discoveries, about the relative abundances of isotopes, that paved the way for geochemical research on the deep past. My thesis is that Nier’s early career, spanning the 1930s and 1940s, illustrates a dynamic relationship in which science and technology co-evolved synergistically. This pattern of research spread beyond Nier—who largely moved on from this research after the 1950s—to develop into a research tradition, initially based at the University of Chicago’s Institute for Nuclear Studies and then spreading to other institutions, notably Caltech, the Carnegie Institution of Washington, and the University of California at Berkeley and San Diego. This tradition made crucial contributions to historical geology, including paleoclimatology, solar system history, and the tectonics revolution.

Unstable cosmic ray nuclei constrain low-diffusion zones in the Galactic disc

ABSTRACT Observations of the vicinity of a variety of galactic gamma-ray sources have indicated a local suppression of diffusivity of cosmic rays (CRs) by up to three orders of magnitude. However, the impact of these low-diffusion zones on global properties of CR transport is, however, only poorly understood. Here, we argue that CR nuclear ratios, like the boron-to-carbon ratio and relative abundances of Beryllium isotopes are sensitive to the filling fraction of such low-diffusion zones and hence their measurements can be used to constrain the typical sizes and ages of such regions. We have performed a careful parameter study of a CR transport model that allows for different diffusion coefficients κdisc and κhalo in the galactic disc and halo, respectively. Making use of preliminary data from the AMS-02 experiment on the ratio of Beryllium isotopes, we find a 3.5σ preference for a suppression of the diffusion coefficient in the disc with a best-fitting value of $\kappa _{\mathrm{disc}}/\kappa _{\mathrm{halo}} = 0.20^{+0.10}_{-0.06}$. We forecast that with upcoming data from the HELIX balloon experiment, the significance could increase to 6.8σ. Adopting a coarse-graining approach, we find that such a strong suppression could be realized if the filling fraction of low-diffusion zones in the disc was $\sim 66~{{\ \rm per\ cent}}$. We conclude that the impact of regions of suppressed diffusion might be larger than usually assumed and ought to be taken into account in models of Galactic CR transport.

Quantifying label enrichment from two mass isotopomers increases proteome coverage for in vivo protein turnover using heavy water metabolic labeling

Heavy water metabolic labeling followed by liquid chromatography coupled with mass spectrometry is a powerful high throughput technique for measuring the turnover rates of individual proteins in vivo. The turnover rate is obtained from the exponential decay modeling of the depletion of the monoisotopic relative isotope abundance. We provide theoretical formulas for the time course dynamics of six mass isotopomers and use the formulas to introduce a method that utilizes partial isotope profiles, only two mass isotopomers, to compute protein turnover rate. The use of partial isotope profiles alleviates the interferences from co-eluting contaminants in complex proteome mixtures and improves the accuracy of the estimation of label enrichment. In five different datasets, the technique consistently doubles the number of peptides with high goodness-of-fit characteristics of the turnover rate model. We also introduce a software tool, d2ome+, which automates the protein turnover estimation from partial isotope profiles.

Mycelial nutrient transfer promotes bacterial co-metabolic organochlorine pesticide degradation in nutrient-deprived environments

Biotransformation of soil organochlorine pesticides (OCP) is often impeded by a lack of nutrients relevant for bacterial growth and/or co-metabolic OCP biotransformation. By providing space-filling mycelia, fungi promote contaminant biodegradation by facilitating bacterial dispersal and the mobilization and release of nutrients in the mycosphere. We here tested whether mycelial nutrient transfer from nutrient-rich to nutrient-deprived areas facilitates bacterial OCP degradation in a nutrient-deficient habitat. The legacy pesticide hexachlorocyclohexane (HCH), a non-HCH-degrading fungus (Fusarium equiseti K3), and a co-metabolically HCH-degrading bacterium (Sphingobium sp. S8) isolated from the same HCH-contaminated soil were used in spatially structured model ecosystems. Using 13C-labeled fungal biomass and protein-based stable isotope probing (protein-SIP), we traced the incorporation of 13C fungal metabolites into bacterial proteins while simultaneously determining the biotransformation of the HCH isomers. The relative isotope abundance (RIA, 7.1–14.2%), labeling ratio (LR, 0.13–0.35), and the shape of isotopic mass distribution profiles of bacterial peptides indicated the transfer of 13C-labeled fungal metabolites into bacterial proteins. Distinct 13C incorporation into the haloalkane dehalogenase (linB) and 2,5-dichloro-2,5-cyclohexadiene-1,4-diol dehydrogenase (LinC), as key enzymes in metabolic HCH degradation, underpin the role of mycelial nutrient transport and fungal-bacterial interactions for co-metabolic bacterial HCH degradation in heterogeneous habitats. Nutrient uptake from mycelia increased HCH removal by twofold as compared to bacterial monocultures. Fungal-bacterial interactions hence may play an important role in the co-metabolic biotransformation of OCP or recalcitrant micropollutants (MPs).

A New Reaction Rate of the 27Al(p/α)24Mg Reaction Based on Indirect Measurements at Astrophysical Energies and Implications for 27Al Yields of Intermediate-mass Stars

The abundance of 26Al carries a special role in astrophysics, since it probes active nucleosynthesis in the Milky Way and constrains the Galactic core-collapse supernovae rate. It is estimated through the detection of the 1809 keV γ-line and from the superabundance of 26Mg in comparison with the most abundant Mg isotope (A = 24) in meteorites. For this reason, high precision is necessary also in the investigation of the stable 27Al and 24Mg isotopes. Moreover, these nuclei enter the so-called MgAl cycle, playing an important role in the production of Al and Mg. Recently, high-resolution stellar surveys have shown that the Mg–Al anticorrelation in red-giant stars in globular clusters may hide the existence of multiple stellar populations, and that the relative abundances of Mg isotopes may not be correlated with Al. The common thread running through these astrophysical scenarios is the 27Al(p,α)24Mg reaction, which is the main 27Al destruction channel and directly correlates its abundance with the 24Mg one. Since available reaction rates show large uncertainties owing to the vanishingly small cross section at astrophysical energies, we have applied the Trojan Horse Method to deduce the reaction rate with no need of extrapolation. The indirect measurement made it possible to assess the contribution of the 84 keV resonance and to lower upper limits on the strength of nearby resonances. In intermediate-mass AGB stars experiencing hot bottom burning, a sizeable increase in surface aluminum abundance is observed at the lowest masses, while 24Mg is essentially unaffected by the change in the reaction rate.

Proteomics-Compatible Fourier Transform Isotopic Ratio Mass Spectrometry of Polypeptides.

Measuring the relative abundances of heavy stable isotopes of the elements C, H, N, and O in proteins is of interest in environmental science, archeology, zoology, medicine, and other fields. The isotopic abundance measurements of the fine structure of immonium ions with ultrahigh resolution mass spectrometry obtained in gas-phase fragmentation of polypeptides have previously uncovered anomalous deuterium enrichment in (hydroxy)proline of bone collagen in marine mammals. Here, we provide a detailed description and validation of this approach and demonstrate per mil-range precision of isotopic ratio measurements in aliphatic residues from proteins and cell lysates. The analysis consists of proteomics-type experiment demanding sub-microgram amounts of a protein sample and providing concomitantly protein sequence data allowing one to verify sample purity and establish its identity. A novel software tool protein amino acid-resolved isotopic ratio mass spectrometry (PAIR-MS) is presented for extracting isotopic ratio data from the raw data files acquired on an Orbitrap mass spectrometer.

The whisper of a whimper of a bang: 2400 d of the Type Ia SN 2011fe reveals the decay of 55Fe

ABSTRACT We analyse new multifilter Hubble Space Telescope (HST) photometry of the normal Type Ia supernova (SN Ia) 2011fe out to ≈2400 d after maximum light, the latest observations to date of a SN Ia. We model the pseudo-bolometric light curve with a simple radioactive decay model and find energy input from both 57Co and 55Fe are needed to power the late-time luminosity. This is the first detection of 55Fe in a SN Ia. We consider potential sources of contamination such as a surviving companion star or delaying the deposition time-scale for 56Co positrons but these scenarios are ultimately disfavored. The relative isotopic abundances place direct constraints on the burning conditions experienced by the white dwarf (WD). Additionally, we place a conservative upper limit of <10−3 M⊙ on the synthesized mass of 44Ti. Only two classes of explosion models are currently consistent with all observations of SN 2011fe: (1) the delayed detonation of a low-ρc, near-MCh (1.2–1.3 M⊙) WD, or (2) a sub-MCh (1.0–1.1 M⊙) WD experiencing a thin-shell double detonation.

Optimizing 40Ar/39Ar analyses using an Isotopx NGX-600 mass spectrometer

40Ar/39Ar geochronology relies on magnetic sector mass spectrometers to determine relative isotopic abundances. Ongoing technological developments within noble gas mass spectrometers over the last decade have led to analysis of increasingly smaller samples and higher precision, but also result in more complex data correction and interpretation. We describe a new multi-collector noble gas spectrometer, the Isotopx NGX-600, that is configured to optimize 40Ar/39Ar measurements. The NGX-600 is equipped with 9 Faraday collectors and one ion counting electron multiplier. Each Faraday is equipped with Isotopx ATONA® amplifier technology, enabling measurements spanning a dynamic range of amplified beam current from below 10−16 A to above 10−9 A. The performance of the NGX-600 is evaluated using both a conventional Nier-type ion source, and a next generation low temperature ion source, which allows for trap current variation from 200 μA to 1000 μA. We have performed over 3000 analyses of atmospheric argon to: (1) assess optimal measurement and integration times for blanks, baselines, and air aliquots of various ion intensities, (2) quantify the sensitivity via measurements of first principles 40Ar/39Ar standards, (3) compare the sensitivity between the conventional and new low temperature Nier-type ion sources, and (4) evaluate corrections associated with inter-Faraday biases, instrumental mass bias, and Faraday-multiplier gain. In addition to optimization experiments, we report a comparative analysis of both single crystal fusion and incremental heating data from Quaternary volcanic rocks obtained using both the 5-collector Nu Instruments Noblesse and the NGX-600 spectrometers.

Exploring the astrophysical energy range of the 27Al[formula omitted]Mg reaction: A new recommended reaction rate

The 26Al abundance holds a special role in present-day astrophysics, since it is a probe of active nucleosynthesis in the Galaxy and a valuable constraint of Galactic core-collapse supernovae rate. It is estimated through the detection of the 1809-keV γ-line of the daughter 26Mg and from the superabundance of 26Mg in comparison with the most abundant 24Mg isotope in meteorites. Accurate knowledge of the reaction rates involving 26Al, its stable counterpart 27Al and 24Mg is then mandatory. Moreover, these nuclei enter the MgAl cycle playing an important role in the production of Al and Mg isotopes. Recently, high-resolution stellar surveys have shown that the Mg-Al anti-correlation in red giants of globular clusters may hide the existence of multiple stellar populations, and that the relative abundances of Mg isotopes may not show correlation with Al.The common thread running through these astrophysical scenarios is the 27Al(p,α)24Mg reaction, which is the main 27Al destruction channel and directly correlates its abundance with the 24Mg one. Since available reaction rates show an order of magnitude uncertainty owing to the vanishingly small cross section at astrophysical energies, we have applied the Trojan Horse Method to deduce the reaction rate with no need of extrapolation. The indirect measurement made it possible to assess the contribution of the 84-keV resonance and to lower the upper limits on the strength of nearby resonances, with potential important impact for astrophysics. In particular, modifications in the 27Al and 24Mg abundances up to ∼30% are predicted for intermediate mass stars.

Multiplexed Cross-Linking with Isobaric Quantitative Protein Interaction Reporter Technology.

Chemical cross-linking with mass spectrometry (XL-MS) has emerged as a useful technique for interrogating protein structures and interactions. When combined with quantitative proteomics strategies, protein conformational and interaction dynamics can be probed. Quantitative XL-MS has been demonstrated with the use of stable isotopes incorporated metabolically or into the cross-linker molecules. Isotope-labeled cross-linkers have primarily utilized deuterium and rely on MS1-based quantitation of precursor ion extracted ion chromatograms. Recently the development and application of isobaric quantitative protein interaction reporter (iqPIR) cross-linkers were reported, which utilize 13C and 15N isotope labels. Quantitation is accomplished using relative fragment ion isotope abundances in tandem mass spectra. Here we describe the synthesis and initial evaluation of a multiplexed set of iqPIR molecules, allowing for up to six cross-linked samples to be quantified simultaneously. To analyze data for such cross-linkers, the two-channel mode of iqPIR quantitative analysis was adapted to accommodate any number of channels with defined ion isotope peak mass offsets. The summed ion peak intensities in the overlapping channel isotope envelopes are apportioned among the channels to minimize the difference with respect to the predicted ion isotope envelopes. The result is accurate and reproducible relative quantitation enabling direct comparison among six differentially labeled cross-linked samples. The approach described here is generally extensible for the iqPIR strategy, accommodating future iqPIR reagent design, and enables large-scale in vivo quantitative XL-MS investigation of the interactome.

Measuring titanium isotope ratios in exoplanet atmospheres

Context. Measurements of relative isotope abundances can provide unique insights into the formation and evolution histories of celestial bodies, tracing various radiative, chemical, nuclear, and physical processes. In this regard, the five stable isotopes of titanium are particularly interesting. They are used to study the early history of the Solar System, and their different nucleosynthetic origins help constrain Galactic chemical models. Additionally, titanium’s minor isotopes are relatively abundant compared to those of other elements, making them more accessible for challenging observations, such as those of exoplanet atmospheres. Aims. We aim to assess the feasibility of performing titanium isotope measurements in exoplanet atmospheres. Specifically, we are interested in understanding whether processing techniques used for high-resolution spectroscopy, which remove continuum information about the planet spectrum, affect the derived isotope ratios. We also want to estimate the signal-to-noise requirements for future observations. Methods. We used an archival high-dispersion CARMENES spectrum of the M-dwarf GJ 1002 as a proxy for an exoplanet observed at very high signal-to-noise. Both a narrow (7045–7090 Å) and wide (7045–7500 Å) wavelength region were defined for which spectral retrievals were performed using petitRADTRANS models, resulting in isotope ratios and uncertainties. These retrievals were repeated on the spectrum with its continuum removed to mimic typical high-dispersion exoplanet observations. The CARMENES spectrum was subsequently degraded by adding varying levels of Gaussian noise to estimate the signal-to-noise requirements for future exoplanet atmospheric observations. Results. The relative abundances of all minor Ti isotopes are found to be slightly enhanced compared to terrestrial values. A loss of continuum information from broadband filtering of the stellar spectrum has little effect on the isotope ratios. For the wide wavelength range, a spectrum with a signal-to-noise of 5 is required to determine the isotope ratios with relative errors ≲10%. Super Jupiters at large angular separations from their host star are the most accessible exoplanets, requiring about an hour of observing time on 8-meter-class telescopes, and less than a minute of observing time with the future Extremely Large Telescope.

Comparison of High-Resolution Fourier Transform Mass Spectrometry Platforms for Putative Metabolite Annotation.

Fourier transform ion cyclotron resonance (FT-ICR) and Orbitrap mass spectrometry (MS) are among the highest-performing analytical platforms used in metabolomics. Non-targeted metabolomics experiments, however, yield extremely complex datasets that make metabolite annotation very challenging and sometimes impossible. The high-resolution accurate mass measurements of the leading MS platforms greatly facilitate this process by reducing mass errors and spectral overlaps. When high resolution is combined with relative isotopic abundance (RIA) measurements, heuristic rules, and constraints during searches, the number of candidate elemental formula(s) can be significantly reduced. Here, we evaluate the performance of Orbitrap ID-X and 12T solariX FT-ICR mass spectrometers in terms of mass accuracy and RIA measurements and how these factors affect the assignment of the correct elemental formulas in the metabolite annotation pipeline. Quality of the mass measurements was evaluated under various experimental conditions (resolution: 120, 240, 500 K; automatic gain control: 5 × 104, 1 × 105, 5 × 105) for the Orbitrap MS platform. High average mass accuracy (<1 ppm for UPLC-Orbitrap MS and <0.2 ppm for direct infusion FT-ICR MS) was achieved and allowed the assignment of correct elemental formulas for over 90% (m/z 75-466) of the 104 investigated metabolites. 13C1 and 18O1 RIA measurements further improved annotation certainty by reducing the number of candidates. Overall, our study provides a systematic evaluation for two leading Fourier transform (FT)-based MS platforms utilized in metabolite annotation and provides the basis for applying these, individually or in combination, to metabolomics studies of biological systems.

Amino Acid δ15N Can Detect Diet Effects on Pollution Risks for Yellow-Legged Gulls Overlooked by Trophic Position

The use of top-consumers as bioindicators of the health of food webs is hampered by uncertainties in their effective use of resources. In this study, the abundance of stable nitrogen isotopes in amino acids from homogenised eggs of the Yellow-legged Gull (Larus michahellis) allowed to identify variations in trophic resource exploitation between geographically adjacent nesting colonies in the Ria de Vigo (NW Spain) that exhibited marked differences in pollutants. Eggs from nests in the Cíes Islands (located in a National Park) showed a large variability in stable carbon and nitrogen isotopes in bulk egg content encompassing that of eggs from Vigo city (a major fishing harbour). However, both colonies differed in the relative concentration and abundance of nitrogen isotopes of lysine, an essential amino acid present in marine prey, but also extensively used in feed stocks for poultry and swine. Notwithstanding the similarity in trophic position for both colonies, gulls from Cíes Islands may have acquired a substantial fraction of lysine from garbage dump sites, while those of the urban colony relied on fish discards. This unexpected conclusion is partly supported by the large variability reported for gull’s diet in this region and calls for detailed estimations of diet when assessing the conservation status and pollution risks of marine ecosystems.

Machine-learning-enhanced time-of-flight mass spectrometry analysis

SummaryMass spectrometry is a widespread approach used to work out what the constituents of a material are. Atoms and molecules are removed from the material and collected, and subsequently, a critical step is to infer their correct identities based on patterns formed in their mass-to-charge ratios and relative isotopic abundances. However, this identification step still mainly relies on individual users' expertise, making its standardization challenging, and hindering efficient data processing. Here, we introduce an approach that leverages modern machine learning technique to identify peak patterns in time-of-flight mass spectra within microseconds, outperforming human users without loss of accuracy. Our approach is cross-validated on mass spectra generated from different time-of-flight mass spectrometry (ToF-MS) techniques, offering the ToF-MS community an open-source, intelligent mass spectra analysis.

Accurate quantification of lipid species affected by isobaric overlap in Fourier-transform mass spectrometry

AbstractLipidomics data require consideration of ions with near-identical masses, which comprises among others the Type-II isotopic overlap. This overlap occurs in series of lipid species differing only by number of double bonds (DBs) mainly because of the natural abundance of 13C-atoms. High-resolution mass spectrometry, such as Fourier-transform mass spectrometry (FTMS), is capable of resolving Type-II overlap depending on mass resolving power. In this work, we evaluated FTMS quantification accuracy of lipid species affected by Type-II overlap. Spike experiments with lipid species pairs of various lipid classes were analyzed by flow injection analysis-FTMS. Accuracy of quantification was evaluated without and with Type-II correction (using relative isotope abundance) as well as utilizing the first isotopic peak (M+1). Isobaric peaks, which were sufficiently resolved, were most accurate without Type-II correction. In cases of partially resolved peaks, we observed peak interference causing distortions in mass and intensity, which is a well-described phenomenon in FTMS. Concentrations of respective species were more accurate when calculated from M+1. Moreover, some minor species, affected by considerable Type-II overlap, could only be quantified by M+1. Unexpectedly, even completely unresolved peaks were substantially overcorrected by Type-II correction because of peak interference. The described method was validated including intraday and interday precisions for human serum and fibroblast samples. Taken together, our results show that accurate quantification of lipid species by FTMS requires resolution-depended data analysis.

LC-HRMS characterization of the skin pigmentation and sexual enhancers melanotan II and bremelanotide sold on the black market of performance and image enhancing drugs.

The spread of performance and image enhancing drugs (PIEDs) often requires forensic toxicology laboratories to identify unknown compounds without reference standards. We characterized the PIEDs melanotan II and bremelanotide, not legally marketed, in eight unknown samples confiscated by police together with anabolic steroids, hormone modulators, sexual enhancers and stimulants, intended for the black market of bodybuilders, using liquid chromatography-high resolution/high accuracy Orbitrap mass spectrometry (LC-HRMS). The characterization was carried out by the accurate mass measurements of MH+ ionic species, the study of their isotopic patterns and the associated relative isotopic abundance (RIA) values, as well as the accurate mass measurements of collision-induced product ions obtained in fragmentation experiments. LC-HRMS confirmed itself as a powerful analytical tool to elucidate the elemental composition and structural characteristics of unknown compounds.