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We studied δ13C, δ15N and δ18O values, and total mercury (THg) concentrations in muscle samples from deep-sea predators - five beaked whale species and sperm whales - stranded along the coast of Hokkaido, in the north of Japan in 2010 and 2019. The δ13C, δ15N and δ18O values, THg concentrations, and body length (BL) of Stejneger's beaked whales were similar to those of Hubbs' beaked whales, which belong to the same genus. In contrast, δ13C values, THg concentrations, and BL of Sato's beaked whales were markedly different from those of Baird's beaked whales, which belong to the same genus. Stejneger's and Hubbs' beaked whales living around Hokkaido may compete in their ecological niches, whereas Sato's and Baird's beaked whales may segregate their ecological niches. Although Cuvier's beaked whales and sperm whales belong to different genera and their BLs were significantly different, their δ13C and δ15N values were similar, probably because they can dive and stay in deeper waters than other beaked whale species. The δ13C values in combined samples from all whales increased with increasing BL, probably owing to the larger whale species' dietary preference for squid. The δ13C values in combined samples from all whales were positively correlated with THg concentrations, whereas the δ15N values in the combined samples were negatively correlated. The δ18O values in combined samples from most whales tended to be positively correlated with THg concentrations. These correlations may be explained by a higher THg load from deep-sea feeding than from pelagic feeding and by a feeding shift towards lower trophic levels.

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Migratory bird populations are declining globally at alarming rates. Non-breeding site conditions affect breeding populations, but generalising non-breeding habitat conditions over large spatial regions cannot address potential fine-scale differences across landscapes or local populations. Plumage characteristics can mediate the effects of environmental conditions on individual fitness. However, whether different phenotypes use distinctive non-breeding sites, and whether they respond to non-breeding site conditions differently remains largely unknown. Stable isotopes (δ13C, δ15N, δ2H) of inert tissues are useful to infer habitat characteristics and geographic origins where those tissues were grown. We collected winter-grown feathers from pied flycatchers (Ficedula hypoleuca) on their breeding grounds over several years from males whose dorsal plumage colouration ranged continuously from brown to black and assessed their stable isotope values as proxies of local habitat conditions. Based on feather δ2H profiles we found that browner males spent their non-breeding season in drier habitats than black males. Assignment to origin analysis shows potential regional non-breeding ground separation between differently coloured males. High within-individual repeatability of both δ13C and δ15N indicate the pied flycatcher males return yearly to similar areas. Blacker males were more likely to return to the breeding grounds after dry years compared with brown males. The opposite was found in wet years. Our study demonstrates that different phenotypes are exposed to different non-breeding site conditions which can differentially affect individual survivorship. This has important ramifications for population dynamics under predicted climate change scenarios where especially brown phenotype pied flycatcher males may be under a risk of decreasing.

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The extraction of lipids by the Folch method from the muscles of all the fish studied led to statistically significant differences in the values of δ15N. At the same time, lipid extraction led to a statistically significant increase in δ13C in pike and roach, and to a statistically insignificant decrease in δ13C in perch and bream. Thus, lipid extraction cannot serve as a universal method of sample preparation for the analysis of the isotopic composition of carbon (13C/12C) and nitrogen (15N/14N) in fish muscles. The differences between the δ13C values in the samples before and after lipid extraction were statistically investigated by different models. It is shown that mathematical correction method models can be used, but the results are depending on the fish types.

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We characterized the elemental and C and N stable isotope compositions of Tillandsia fasciculata Sw., Tillandsia balbisiana Schult. & Schult.f. and Tillandsia recurvata (L.) L. samples collected in Cienfuegos (Cuba). Results showed high enrichment factors for S, Hg, Cd, Pb, P, Zn, Cu, Mo, Sb and Ca in all Tillandsia species, indicating inputs from local anthropogenic activities (road traffic, industries and cement production). Carbon concentrations and δ13C varied from 38.3-47.7 % and -20.4 to -13.4 ‰ within the three species, respectively. δ13C showed seasonal dependence with the dry and wet periods and more 13C-depleted values in urban/industrial areas, coherent with the input of anthropogenic emissions. Nitrogen concentrations (0.4-1.3 %) and δ15N values (-9.9-4.4 ‰) exhibit larger variations and are positively correlated in the three species. The most positive δ15N in T. recurvata (-0.2-4.4 ‰) are attributed to contributions from industrial activities and road traffic. In fact, both δ15N and total nitrogen (TN) values increase in sites with higher road traffic and show significant correlations with typical road traffic and industrial tracers. Finally, we calculate an average total nitrogen deposition rate of 4.4 ± 2.3 kg ha-1 a-1 from N content in T. recurvata, similar to the existing values determined in the region by field measurements, but higher than the global terrestrial average.

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In order to study the trophic level of small tuna species and their contribution to the carbon flow in pelagic food webs, an analysis of carbon and nitrogen stable isotopes was carried out. The investigation was focused on four small tuna species (Auxis rochei, Auxis thazard, Euthynnus alletteratus and Sarda sarda) commonly harvested in the northeast Atlantic Ocean. The isotope analysis showed how the results for S. sarda are different from the rest of the species analysed, with a higher trophic level, similar to other major tuna species. The greatest niche overlap in δ13C and δ15N occurs among A. rochei, A. thazard and E. alletteratus. Auxis rochei and E. alletteratus showed a size-dependent variability in δ15N, and in δ13C for S. sarda. The small tuna S. sarda exhibits the highest migration rates among various geographical areas in comparison to other small pelagic tunas, and the seasonal variability of isotope values in the area studied can be attributed to the incorporation of larger individuals with a higher lipid content. The results of this work provide new information on the ecological role played by small tuna in food webs, which is more complex and varied than currently thought. This knowledge is essential for a more effective management of fisheries.

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Stable isotope labeled Iclepertin (BI 425809, 1) and its major metabolites are needed as internal standards in bioanalytical studies. BI 425809 consists of two main building blocks, 5-methylsulfonyl-2-[(1R)-2,2,2-trifluoro-1-methyl-ethoxy]benzoic acid (2) and 3-[(1R,5R)-3-azabicyclo[3.1.0]hexan-5-yl]-5-(trifluoromethyl)isoxazole (3) linked to each other via an amide bond. We used fluoro[13 C6 ]benzene as the starting material in the preparation of [13 C6 ]-2. This intermediate was then employed to access carbon 13 labeled Iclepertin ([13 C6 ]-1) and other metabolites. The major metabolite BI 761036 (6), which resulted from cytochrome P450 oxidation and amide hydrolysis of BI 425809, was prepared labeled with carbon 13 and nitrogen 15 via two synthetic routes. In the first route, diethyl [13 C3 ]malonate, [13 C]methyl iodide, and hydroxyl[15 N]amine were used to provide [13 C4 ,15 N]-BI 761036 ([13 C4 ,15 N]-6a) in 13 steps in 6% overall yield, whereas in the second route, [13 C3 ]propargyl alcohol, potassium [13 C]cyanide, and [15 N]ammonia were used to furnish [13 C4 ,15 N]-BI 761036 ([13 C4 ,15 N]-6b) in 11 steps in 1% overall yield. The detailed stable isotope synthesis of 1 and its major metabolites is described.

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A novel simplified method is presented for the estimation of the metabolism of plasma proteins (albumin, fibrinogen, α, ß and γ-globulin, glycoprotein) with regard to the whole body protein metabolism in a young male volunteer (22 years, 81 kg body mass). This method is based on multiple oral administration of [15N]glycine followed by measurement of 15N in plasma proteins, total free amino acids, urea and excreted urinary N. The fractional synthesis rate of albumin was estimated to 6.8 % d-1 based on amino acids and 3.3 % d-1 based on urea, respectively. The fractional synthesis rate of the other plasma proteins ranged from 4.3 % d-1 (γ-globulin) to 26.4 % d-1 (α-globulin, fibrinogen). We conclude that the simplified approach using [15N]glycine provides results which are similar to results based on the simultaneously applied 131I-human serum albumin technique as 'gold standard' and to those reported in literature. The compartmental analysis considering comprehensive tracer kinetic data ensures reliable data treatment and enables statistical evaluation. The analytical effort is minimal because the 15N enrichment of plasma protein after chemical digestion may be directly used. Therefore, the novel stable isotope 15N method is suitable for studies in clinical and nutritional research and practice.

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Stable isotope (δ2H, δ13C) measurements of wing tissue have been used to determine the natal geographic origin of migrant monarch butterflies that overwinter in Mexico. This study examines the possibility of using δ13C and δ15N to identify the milkweed habitat used by monarchs in their natal region. Milkweeds were common in corn and soybean fields before herbicide use led to their extirpation around 2006, and the loss of those milkweeds has been proposed as a reason for the monarch population decline. If crop-field monarchs can be identified, then historical samples of monarchs could be examined to test that hypothesis. The δ15N and δ13C values of leaves from milkweeds growing in corn fields, soybean fields and non-agricultural habitats were examined as well as monarchs that were raised on those leaves. There were no δ15N values for leaves or monarchs that were distinctive for crop fields. Milkweeds in corn fields, and monarchs that were raised on those milkweeds, were found to have δ13C values distinctly lower than those of other habitats and unlike those of locations within the summer breeding range. Thus, it should be possible to identify monarchs that came from cornfields in samples of overwintering monarchs made before ca. 2006.

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Aerial insectivorous birds have suffered steep population declines in North America over the last 60 years. A lack of information on migratory connectivity between breeding and non-breeding grounds for these species limits our ability to interpret factors affecting their population-specific trends. We determined likely Latin American non-breeding regions of Bank (Riparia riparia), Barn (Hirundo rustica) and Cliff (Petrochelidon pyrrhonota) swallow from populations across their breeding ranges. We used predicted feather hydrogen (δ2Hf) and carbon (δ13Cf) isoscapes for winter-grown feathers to indicate areas of highest probability of moult origin and incorporated these results into a cluster analysis to determine likely broad non-breeding regions. We also assessed variation in wing length among populations to determine the potential for this metric to differentiate population moult origins. We then investigated patterns of multi-isotopic (δ2Hf, δ13Cf, δ15Nf) and wing-length niche occupancy by quantifying niche size and overlap among populations under the assumption that broad niches were consistent with low within-species migratory connectivity and narrow and non-overlapping niches with higher connectivity. Multivariate assignment identified different non-breeding regions and potential clusters of moult origin generally corresponding to Central America and northern South America, eastern and south-central South America, and the western and southern part of that continent, with variation within and among populations and species. Separate niche space indicated different wintering habitat or areas used by species or populations whereas niche overlap indicated only potential spatial similarity. Wing length varied significantly among populations by species, being longer in the west and north for Bank and Cliff Swallow and longer in eastern Canadian Barn Swallow populations. Barn Swallow occupied consistently larger isotopic and wing length niche space than the other species. Comparisons among populations across species showed variable isotopic and wing-length niche overlap generally being greater within breeding regions and lower between western and eastern breeding populations supporting a general North American continental divide for all species with generally low migratory connectivity for all species. We present a novel approach to assessing connectivity using inexpensive and broad isotopic approaches that provides the basis for hypothesis testing using more spatially explicit expensive techniques.

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Strandings of striped dolphins (SD) and short-finned pilot whales (PW) in Hokkaido, northern Japan, are rare but have recently increased, probably due to global warming. We quantified δ13C, δ15N, and δ18O in muscles of SD (n = 7) and PW (n = 3) stranded in Hokkaido and compared these values with those in muscles (red meat products) of hunted SD and PW in three areas of central and southern Japan. δ18O in stranded SD, except for the calf, decreased with increasing body length (BL), whereas δ13C increased, with no BL-related changes in δ15N. The variability of δ18O (range of maximum and minimum) was larger in the stranded SD (7.5 ‰) than of the hunted SD in three areas (0.9, 1.9, and 1.4 ‰), whereas that of δ15N was smaller in the stranded SD than in the hunted SD. Similarly, the variability of δ18O was larger in the stranded PW in Hokkaido (3.3 ‰) than in the hunted PW in central Japan (1.4 ‰). The larger variability of δ18O and smaller variability of δ15N in stranded SD imply long-term sojourning in coastal waters and feeding on small amounts of limited prey species at low trophic levels before death.

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The Northern shoveler, Spatula clypeata, makes several migratory stopovers to reach its breeding site in the best conditions. These stopovers allow the species to replenish their reserves. Therefore, feeding efficiency at such sites is essential. Despite its importance, few studies have been conducted on the spring ecology of the shoveler, particularly on its diet at stopover sites. Therefore, this study focused on the Northern shoveler's feeding habit during its spring migratory stopover in the Marais breton (MB), a wetland situated in Vendée (France, Atlantic coast). The shoveler's plasma and potential food resources were studied using a stable carbon and nitrogen isotope analysis. The study showed that the shoveler feeds primarily on microcrustaceans, especially Cladocera and Copepoda; Chironomidae larvae, Corixidae, Hydrophilidae larvae, and particulate organic matter. This last food source, the POM, had never been highlighted before.

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The nitrogen and oxygen (δ15N, δ18O, δ17O) stable isotopic compositions of nitrate (NO3-) are crucial tracers of nutrient N sources and dynamics in aquatic and atmospheric systems. Methods to reduce aqueous NO3- to N2O gas (microbial or Cd method) before 15N and 18O isotope analyses require multi-step conversion or toxic chemicals, and 17O in N2O cannot be disentangled by IRMS due to isobaric interferences. This technical note describes the automation of the stable-isotope analyses of nitrate by coupling the new Ti method with a headspace autosampler and an N2O triple-isotope laser analyzer based on off-axis integrated cavity output spectroscopy. The automation yielded accurate and precise results for routine determinations of δ15N, δ18O, and δ17O values for aqueous nitrate in environmental waters. Systematic corrections were required for cavity pressure, N2O concentration and water vapour content to obtain the highest precision for all three isotopic ratios. For the first time, an automated laser-based system facilitates routine low-cost triple isotope analyses in studies where high-temporal resolution isotope analyses of NO3- are required but have been, until now, cost-prohibitive and time-consuming (e.g. atmospheric N pollution).

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We report dissolution Dynamic Nuclear Polarization (d-DNP) of [15 N3 ]metronidazole ([15 N3 ]MNZ) for the first time. Metronidazole is a clinically approved antibiotic, which can be potentially employed as a hypoxia-sensing molecular probe using 15 N hyperpolarized (HP) nucleus. The DNP process is very efficient for [15 N3 ]MNZ with an exponential build-up constant of 13.8 min using trityl radical. After dissolution and sample transfer to a nearby 4.7 T Magnetic Resonance Imaging scanner, HP [15 N3 ]MNZ lasted remarkably long with T1 values up to 343 s and 15 N polarizations up to 6.4 %. A time series of HP [15 N3 ]MNZ images was acquired in vitro using a steady state free precession sequence on the 15 NO2 peak. The signal lasted over 13 min with notably long T2 of 20.5 s. HP [15 N3 ]MNZ was injected in the tail vein of a healthy rat, and dynamic spectroscopy was performed over the rat brain. The in vivo HP 15 N signals persisted over 70 s, demonstrating an unprecedented opportunity for in vivo studies.

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This mini-review covers the use of nitrogen-15 in bacterial and fungal natural product discovery and biosynthetic characterization from 1970 to 2022. Nitrogen is an important element in a number of bioactive and structurally intriguing natural products including alkaloids, non-ribosomal peptides, and hybrid natural products. Nitrogen-15 can be detected at natural abundance utilizing two-dimensional nuclear magnetic resonance and mass spectrometry. Additionally, it is a stable isotope that can be added to growth media for both filamentous fungi and bacteria. With stable isotope feeding, additional two-dimensional nuclear magnetic resonance and mass spectrometry strategies have become available, and there is a growing trend to use nitrogen-15 stable isotope feeding for the biosynthetic characterization of natural products. This mini-review will catalog the use of these strategies, analyze the strengths and weaknesses of the different approaches, and suggest future directions for the use of nitrogen-15 in natural product discovery and biosynthetic characterization.

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Global climate change is causing abiotic shifts such as higher air and ocean temperatures, and disappearing sea ice in Arctic ecosystems. These changes influence Arctic-breeding seabird foraging ecology by altering prey availability and selection, affecting individual body condition, reproductive success, and exposure to contaminants such as mercury (Hg). The cumulative effects of alterations to foraging ecology and Hg exposure may interactively alter the secretion of key reproductive hormones such as prolactin (PRL), important for parental attachment to eggs and offspring and overall reproductive success. However, more research is needed to investigate the relationships between these potential links. Using data collected from 106 incubating female common eiders (Somateria mollissima) at six Arctic and sub-Arctic colonies, we examined whether the relationship between individual foraging ecology (assessed using δ13C, δ15N) and total Hg (THg) exposure predicted PRL levels. We found a significant, complex interaction between δ13C, δ15N and THg on PRL, suggesting that individuals cumulatively foraging at lower trophic levels, in phytoplankton-dominant environments, and with the highest THg levels had the most constant significant relationship PRL levels. Cumulatively, these three interactive variables resulted in lowered PRL. Overall, results demonstrate the potential downstream and cumulative implications of environmentally induced changes in foraging ecology, in combination with THg exposure, on hormones known to influence reproductive success in seabirds. These findings are notable in the context of continuing environmental and food web changes in Arctic systems, which may make seabird populations more susceptible to ongoing stressors.

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Eurasian red squirrels Sciurus vulgaris have unusually high δ13C values compared to other forest rodents, which is seemingly related to the consumption of 13C-enriched conifer seeds. To test this hypothesis, we analyzed the hair of wild and zoo-kept red squirrels, seeds of pine and spruce, and feathers of specialized and opportunistic consumers of conifer seeds, crossbills Loxia spp., and woodpeckers Dendrocopos major. Data on the isotopic composition (δ13C and δ15N values) of hair or feathers of other species of forest rodents and birds were obtained from published studies. The range of mean δ13C values of hair of wild forest rodents (19 species) exceeded 10 ‰. All squirrel species had high 13C content, S. vulgaris having maximum δ13C values. In contrast, S. vulgaris kept in captivity had an isotopic composition similar to other captive rodents. The feathers of crossbills were enriched in 13C compared to other forest birds (15 species), while seeds of coniferous trees often had higher δ13C values compared to seeds of other woody plants. Distinctiveness of the isotopic composition of mammals and birds feeding on the seeds of coniferous trees suggests that this resource can be traced through the entire forest food web.

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Investigating the sources, migration and proportional contribution of nitrate is essential to effectively protect water quality. δ15N-NO3-, δ18O-NO3- and Stable Isotope Analysis in R (SIAR) were used to qualitatively and quantitatively analyse nitrate sources in the Pingzhai Reservoir water body. The values of δ15N-NO3- and δ18O-NO3- in water vary with season. Soil organic nitrogen and chemical fertilisers are the main sources of nitrate in autumn, while domestic sewage and livestock manure are the primary sources of nitrate in winter and spring. The SIAR results showed that chemical fertilisers, livestock manure, sewage, and soil organic nitrogen had the highest proportional contribution. In autumn, the proportional contribution of chemical fertilisers to river and reservoir were 47 and 51 %. During winter, the proportional contributions of livestock manure and sewage to river and reservoir were 53 and 68 %, respectively, and in spring 49 and 68 %, respectively. Considering the fragility of karst ecosystems, strict measures should be formulated for the use of chemical fertilisers and standards for sewage discharge should be raised. Control nitrogen input from agricultural activities and prevent water quality deterioration.

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Stable isotope ratios of nitrogen and oxygen (15N/14N and 18O/16O) of nitrate (NO3-) are excellent tracers for developing systematic understanding of sources, conversions, and deposition of reactive atmospheric nitrogen (Nr) in the environment. Despite recent analytical advances, standardized sampling of NO3-) isotopes in precipitation is still lacking. To advance atmospheric studies on Nr species, we propose best-practice guidelines for accurate and precise sampling and analysis of NO3- isotopes in precipitation based on the experience obtained from an international research project coordinated by the International Atomic Energy Agency (IAEA). The precipitation sampling and preservation strategies yielded a good agreement between the NO3- concentrations measured at the laboratories of 16 countries and at the IAEA. Compared to conventional methods (e.g., bacterial denitrification), we confirmed the accurate performance of the lower cost Ti(III) reduction method for isotope analyses (15N and 18O) of NO3- in precipitation samples. These isotopic data depict different origins and oxidation pathways of inorganic nitrogen. This work emphasized the capability of NO3- isotopes to assess the origin and atmospheric oxidation of Nr and outlined a pathway to improve laboratory capability and expertise at a global scale. The incorporation of other isotopes like 17O in Nr is recommended in future studies.

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Stable carbon (δ13C) and nitrogen (δ15N) isotopic compositions of bone and dentine collagen extracted from museum specimens have been widely used to study the paleoecology of past populations. Due to possible systematic differences in stable isotope values between bone and dentine, dentine values need to be transformed into bone-collagen equivalent using a correction factor to allow comparisons between the two collagen sources. Here, we provide correction factors to transform dentine δ13C and δ15N values into bone-collagen equivalent for two toothed whales: narwhal and beluga. We sampled bone and dentine from the skulls of 11 narwhals and 26 belugas. In narwhals, dentine was sampled from tusk and embedded tooth; in belugas, dentine was sampled from tooth. δ13C and δ15N were measured, and intra-individual bone and dentine isotopic compositions were used to calculate correction factors for each species. We detected differences in δ13C and δ15N. In both narwhals and belugas, we found lower average δ13C and δ15N in bone compared with dentine. The correction factors provided by the study enable the combined analysis of stable isotope data from bone and dentine in these species.

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Nitrate stable isotopes provide information about nitrate contamination and cycling by microbial processes. The Fischa-Dagnitz (Austria) spring and river system in the agricultural catchment of the Vienna basin shows minor annual variance in nitrate concentrations. We measured nitrate isotopes (δ15N, δ18O) in the source spring and river up to the confluence with the Danube River (2019-2020) with chemical and water isotopes to assess mixing and nitrate transformation processes. The Fischa-Dagnitz spring showed almost stable nitrate concentration (3.3 ± 1.0 mg/l as NO3--N) year-round but surprisingly variable δ15N, δ18O-NO3- values ranging from +5.5 to +11.1‰ and from +0.5 to +8.1‰, respectively. The higher nitrate isotope values in summer were attributed to release of older denitrified water from the spring whose isotope signal was dampened downstream by mixing. A mixing model suggested denitrified groundwater contributed > 50 % of spring discharge at baseflow conditions. The isotopic composition of NO3- in the gaining streams was partly controlled by nitrification during autumn and winter months and assimilation during the growing season resulting in low and high δ15N-NO3- values, respectively. NO3- isotope variation helped disentangle denitrified groundwater inputs and biochemical cycling processes despite minor variation of NO3- concentration.

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