Stable Isotope Ratio Measurements Research Articles

CO2 conversion to CO by fluidized bed biomass gasification: Measuring CO2 utilization via stable carbon isotope ratios

Thermochemical conversion of CO2 in biomass gasification is a promising technology for utilizing CO2 as a feedstock to produce a CO-rich gas. Simultaneous decomposition reactions of biomass and various gas-solid and gas-gas reactions form the product gas in this process. The overlap in sub-processes makes it challenging to assess the conversion of feedstock CO2 with common methods like mass balancing. This work introduces stable carbon isotope ratio analysis (δ13C) to identify the sourcing of carbonaceous product gas components and determine the conversion of CO2. This methodology is applied to evaluate experiments conducted for one hour of continuous operation in a lab-scale fluidized bed gasifier. Softwood pellets and wood char are used as fuel, with Olivine as a bed material, a target heating temperature of 1000 °C and atmospheric pressure. Product gas with more than 80 vol% CO was generated when wood char was used as fuel. Stable carbon isotope measurements show that CO2 is converted at 48–93% in this process, underpinning the position of biomass CO2 gasification as carbon capture and utilization technology. These results were up to 25% higher than suggested by mass balancing, with higher discrepancies at lower CO2 conversions when using softwood as fuel. Therefore, stable carbon isotope ratio measurement can be a valuable tool for improving the process understanding of biomass CO2 gasification. The results can be used for carbon accounting and the technical development of gasifiers with high CO2 utilization efficiency.

Isotope ratios of total C, N, and S in particulate matter simultaneously calibrated by mixed USGS and IAEA reference materials

This study presents a method for calibrating the isotope ratios of the total carbon, nitrogen, and sulfur in particulate matter (PM) collected from the Seoul metro using an elemental analyzer-isotope ratio mass spectrometer (EA-IRMS). Mixtures of isotope reference materials (MRMs) from the U.S. Geological Survey (USGS) and International Atomic Energy Agency (IAEA) reference materials formed an input dataset for generalized least squares (GLS) regression to yield calibration lines. The analytical method proposed in this study enabled the measurement of stable isotope ratios of total carbon, nitrogen, and sulfur simultaneously. Results showed good linearity and repeatability for carbon and nitrogen isotopes, but poor results for sulfur isotopes due to peak broadening. Reference values with uncertainties for the isotope ratios of total carbon, nitrogen, and sulfur were determined for the collected PM, demonstrating twice as much uncertainty as that of the USGS and IAEA reference materials. Homogeneity was the biggest uncertainty source for the calibrated values.

Diagenetic history of calcite fractures in Vaca Muerta shales (Argentina) inferred from paired Δ47 and fluid inclusion geothermometry

Many low-permeability, hydrocarbon-bearing rocks are productive for petroleum because natural fractures enhance hydrocarbon delivery to wellbores. Exploration and development decisions often must be made in the face of uncertainty about the presence and properties of natural fractures at scales of beds, field and plays, and how they contribute to production. Fractures patterns in subsurface rocks are challenging to predict or characterize owing to the difficulty in obtaining representative samples of fractures and the sparse set of tools for reconstructing how and when fractures grow during sedimentary basin evolution. In this study, we investigate bed-parallel fracture diagenesis in the Vaca Muerta shales (Argentina) based on a set of calcite vein collected from core across a thermal maturity sequence that ranges from the oil to dry gas window. We characterize these samples using secondary ions mass spectrometry (SIMS) measurements of stable isotope ratios, carbonate clumped isotope geothermometry and fluid inclusion analysis. These measurements precisely reconstruct the evolution of fluid geochemistry, temperature and pore fluid pressure during fracture opening. Here we show that within each studied site, all bedding parallel fibrous veins calcite formed at similar ranges of temperature. The fracture mineralization temperature increases substantially at the basin scale, from 90 °C to 120 °C, correlated with host-rock thermal maturity. We compare our constraints on carbonate and fluid temperature with apatite fission track thermal models and find that most of the fractures of the Vaca Muerta shales have formed in a relatively early stage of subsidence of the basin (c.a. 90 to 70 Ma). These ages estimations are consistent with recently published U–Pb ages on calcite veins from the outcropping area (117–61 Ma). The presence of petroleum inclusions (oil, condensate, and gas) in most of the vein's calcite fibers from cores also provides clear evidence that fracture formation was contemporaneous or posterior with petroleum generation, constraining the timing of catagenesis in the Vaca Muerta. Reconstructed paleo pressures conditions of veins formation from fluid inclusion analysis highlight significant fluid overpressure in the shale interval, which likely contributed to fracture initiation and growth. Preserved apparent Δ47 temperatures in fibrous veins carbonates mineralization evolves gradually from 130 °C to 175 °C with increasing host rock thermal maturity. These clumped-isotope-based temperatures are systematically higher than trapping temperatures of associated fluid inclusions; one interpretation of this observation is that carbonate clumped isotope compositions re-equilibrated to near maximum burial conditions by solid-state isotopic re-ordering, yielding a record of the maximum burial temperature the shale unit experienced. The combination of paleothermometry techniques used in this study illustrates the importance of simultaneously exploring several independent geothermometers, particularly the informative combination of fluid inclusion and clumped isotope constraints, which provides a means of understanding the complex diagenesis of old sedimentary rocks that have experienced burial temperatures in the oil and gas thermal windows.

Long-term performance of simultaneous measurement of stable isotopes of oxygen and carbon in cellulose with a high-temperature pyrolysis/gas chromatography/isotope ratio mass spectrometry system at the Institute for Geological and Geochemical Research

AbstractA high-temperature pyrolysis/gas chromatography/isotope ratio mass spectrometry system was established at the Institute for Geological and Geochemical Research in 2013. A dedicated field of application of the system is the simultaneous measurement of stable carbon and oxygen isotope ratios in the cellulose of modern, relict and subfossil plant tissues and sediments. The measurement protocol was fine-tuned during the first year of operation and documented in detail in this report. To quantify the long-term reproducibility of the simultaneous measurement of stable isotopes of oxygen and carbon in cellulose, a 2σ range inferred from repeated measurements of a Quality Assurance standard can be recommended: 0.16 and 0.20‰, for δ13C and δ18O, respectively. An extensive set of samples with known pyrolysis-based δ13C data was analyzed in combustion mode and the paired results were used to assess the necessity of adjustment of the pyrolysis-based δ13C measurements. The variances of the two datasets were not significantly different; the slope (intercept) of the regression was indistinguishable from unity (zero), suggesting that probably owing to the relatively frequent cleaning of the pyrolysis furnace, pyrolysis-based δ13C data neither suffer from a variance bias nor require a specific adjustment.

Relationship between isotope ratios in precipitation and stream water across watersheds of the National Ecological Observation Network

AbstractThe timescales associated with precipitation moving through watersheds reveal processes that are critical to understanding many hydrologic systems. Measurements of environmental stable water isotope ratios (δ2H and δ18O) have been used as tracers to study hydrologic timescales by examining how long it takes for incoming precipitation tracers become stream discharge, yet limited measurements both spatially and temporally have bounded macroscale evaluations so far. In this observation driven study across North American biomes within the National Ecological Observation Network (NEON), we examined δ18O and δ2H stable water isotope in precipitation (δP) and stream water (δQ) at 26 co‐located sites. With an average 54 precipitation samples and 139 stream water samples per site collected over 2014–2022, assessment of local meteoric water lines and local stream water lines showed geographic variation across North America. Taking the ratio of estimated seasonal amplitudes of δP and δQ to calculate young water fractions (Fyw), showed a Fyw range from 1% to 93% with most sites having Fyw below 20%. Calculated mean transit times (MTT) based on a gamma convolution model showed a MTT range from 0.10 to 13.2 years, with half of the sites having MTT estimates lower than 2 years. Significant correlations were found between the Fyw and watershed area, longest flow length, and the longest flow length/slope. Significant correlations were found between MTT and site latitude, longitude, slope, clay fraction, temperature, precipitation magnitude, and precipitation frequency. The significant correlations between water timescale metrics and the environmental characteristics we report share some similarities with those reported in prior studies, demonstrating that these quantities are primarily driven by site or area specific factors. The analysis of isotope data presented here provides important constraints on isotope variation in North American biomes and the timescales of water movement through NEON study sites.

Low‐Coherence Photothermal Interferometry for Precision Spectroscopic Gas Sensing

AbstractLaser spectroscopy has shown great potential as a cost‐effective method for trace gas detection with high sensitivity and specificity. However, it still falls short in applications such as the measurement of stable isotope ratios, which require high precision and stability. Here, ultrasensitive gas detection with remarkable precision and stability as well as better immunity to isobaric interference is demonstrated by use of low‐coherence photothermal interferometry. With a 10 cm long hollow‐core fiber, acetylene detection is achieved with a noise‐equivalent concentration of 0.7 part‐per‐billion and measurement precision of 0.025%. The instability of the detection over a period of 3 h is ±0.038%, 10 times better than the state‐of‐the‐art photothermal spectroscopy. The measurement of the 13C/12C isotope ratio of acetylene is demonstrated with measurement precision of ≈0.01%. This study highlights the potential of low‐coherence photothermal interferometry as an alternative to mass spectrometers, offering reliable gas detection in a compact form.

A year-round observation of δ13C of dicarboxylic acids and related compounds in fine aerosols: Implications from Central European background site

Isotopic analysis of specific compounds in aerosols can be a useful tool when studying atmospheric processes. Here, we present the results of stable carbon isotope ratio (δ13C) measurements performed on a one-year set (n = 96, Sep. 2013–Aug. 2014) of dicarboxylic acids and related compounds in PM1 at a rural Central European background site, Košetice (Czech Republic).The most 13C enriched acid was oxalic (C2, annual average = −16.6 ± 5.0‰) followed by malonic (C3, avg. = −19.9 ± 6.6‰) and succinic (C4, avg. = −21.3 ± 4.6‰) acids. Thus, δ13C values decreased with an increase in carbon numbers. Azelaic acid (C9, avg. = −27.2 ± 3.6‰) was found to be the least 13C enriched.A comparison of δ13C of dicarboxylic acids from other background sites, especially in Asia, shows similar values to those from the European site. This comparison also showed that C2 is more 13C enriched at background sites than at urban ones. In general, we did not observe significant seasonal differences in δ13C values of dicarboxylic acids at the Central European station. We observed statistically significant differences (p value < 0.05) between winter and summer δ13C values solely for C4, glyoxylic acid (ωC2), glutaric acid (C5) and suberic acid (C8).The only significant correlations between δ13C of C2 and δ13C of C3 were found in spring and summer, suggesting that the oxidation of C3 to C2 is significant in these months with a strong contribution from biogenic aerosols. The strongest season-independent annual correlation was observed in δ13C values between C2 and C4, the two dominant dicarboxylic acids. Therefore, C4 appears to be the main intermediate precursor of C2 throughout the whole year.

Oxygen and chlorine isotope fractionation during microbial perchlorate reduction in static and flow through systems

Perchlorate (ClO4−) is an oxyanion with both anthropogenic and natural sources that is widespread on earth and throughout the solar system. Stable isotope ratio measurements are a powerful tool to assess the origin and predict the fate of perchlorate in the environment. The aim of this study was to perform an experimental survey of parameters that influence microbial O and Cl isotope fractionation during microbial perchlorate reduction, covering microbiological (genetic background and community context) and environmental (temperature, salinity, electron donor type and limitation) factors. A new method for the purification of perchlorate for isotope ratio mass spectrometry (IRMS) was developed to allow for more efficient sample preparation and suitable for samples containing small amounts of perchlorate (0.4–2 mg). Although most experiments, regardless of treatment, yielded a consistent isotope enrichment factor ratio (Λ = ε18O/ε37Cl ∼ 2.5), a greater variability was observed of individual isotope enrichment factors (ε18O and ε37Cl). Although most experiments yielded isotope enrichment factors (epsilon) in the larger negative range of previously published values, smaller negative values of ε18O and ε37Cl were observed for a halophilic isolate, Haloarcula marismortui, (ε18O = −15 to −22‰ and ε37Cl = −5 to −7‰), and in sediment column experiments (ε18O = −4 to −15‰ and ε37Cl = −1 to −6‰). Given the complexity of isolating individual parameters from our proposed model, we view our dataset as a survey that points to future opportunities where a particular parameter could be isolated to better understand controls on O and Cl isotope fractionation during microbial perchlorate reduction.

The association between carbon and nitrogen stable isotope ratios of human hair and hypertension

BackgroundThe relationship between stable isotope ratios and dietary protein sources has been reported. However, few studies have examined the effect of stable isotope ratios on metabolic risk in humans. We investigated whether the stable isotope ratios of carbon and nitrogen in human hair are associated with blood pressure and hypertension.MethodsWe conducted a cross-sectional study of 392 subjects (228 men and 164 women). Hair samples of the subjects were used for the measurement of stable isotope ratios of carbon (δ13C) and nitrogen (δ15N).ResultsThe δ13C and δ15N values showed positive correlations with diastolic blood pressure in the subjects without antihypertensive medication. In the subjects without antihypertensive medication, the multivariable-adjusted odds ratio (95% confidence interval) for hypertension was 1.55 (1.04–2.30) per 1‰ increase in δ15N and 1.22 (0.86–1.73) per 1‰ increase in δ13C, respectively. However, in the subjects with antihypertensive medication, neither δ13C nor δ15N values showed a significant association with hypertension.ConclusionsThe stable isotopic ratio of nitrogen in scalp hair is independently associated with hypertension in subjects without antihypertensive medication. The hair δ15N value might be used as a surrogate marker to screen a high-risk population for hypertension.

PS-BPP06-6: THE ASSOCIATION BETWEEN CARBON AND NITROGEN STABLE ISOTOPE RATIOS OF HUMAN HAIR AND HYPERTENSION

Background: The relationship between stable isotope ratios and dietary protein sources has been reported. However, few studies have examined the effect of stable isotope ratios on metabolic risk in humans. We investigated whether the stable isotope ratios of carbon and nitrogen in human hair are associated with blood pressure and hypertension. Methods: We conducted a cross-sectional study of 392 subjects (228 men and 164 women). Hair samples of the subjects were used for the measurement of stable isotope ratios of carbon (Δ13C) and nitrogen (Δ15N). Results: The Δ13C and Δ15N values showed positive correlations with diastolic blood pressure in the subjects without antihypertensive medication. In the subjects without antihypertensive medication, the multivariable-adjusted odds ratio (95% confidence interval) for hypertension was 1.55 (1.04 - 2.30) per 1‰ increase in Δ15N and 1.22 (0.86 - 1.73) per 1‰ increase in Δ13C, respectively. However, in the subjects with antihypertensive medication, neither Δ13C nor Δ15N values showed a significant association with hypertension. Conclusions: The stable isotopic ratio of nitrogen in scalp hair is independently associated with hypertension in subjects without antihypertensive medication. The hair Δ15N value might be used as a surrogate marker to screen a high-risk population for hypertension.

Marine subsidies produce cactus forests on desert islands

In island systems, nitrogen-rich seabird guano is a marine subsidy that can shape terrestrial plant communities. In zones of nutrient upwelling such as the Gulf of California, copious seabird guano is commonplace on bird islands. Several bird islands host regionally unique cactus forests, especially of the large columnar cactus, cardón (Pachycereus pringlei). We show that a chain of interactions across the land-sea interface yields an allochthonous input of nitrogen in the form of seabird guano, fueling the production of some of the densest cactus populations in the world. Fish, seabird, guano, soil, and cactus samples were taken from the representative seabird island of San Pedro Mártir for nitrogen stable isotope ratio measurements, which were compared to soil and cactus samples from other seabird and non-seabird Gulf islands and terrestrial ecosystems throughout the range of the cardón. Isla San Pedro Mártir δ15N values are distinctively high, ranging from fish + 17.7, seabird + 19.7, guano + 14.8, soil + 34.3 and cactus + 30.3 compared to average values across non-bird sites of + 13.0 (N = 213, S.D. = 3.7) for soil and + 9.8 (N = 212, S.D. = 3.4) for cactus. These δ15N values are among the highest ever reported for plants. Seabird island soil and cactus δ15N values were consistently significantly enriched relative to mainland and non-bird islands, a relationship expected due to the progressive volatilization of 14N rich ammonia from decomposing guano deposits. Our findings demonstrate that seabird-mediated marine nutrient deposits provide the source for solubilized nitrogen on desert islands, which stimulate terrestrial plant production in the cardón cactus beyond that seen in either mainland ecosystems or non-seabird islands.

Characterization of vanillin carbon isotope delta reference materials

Stable carbon isotope ratio measurements are used to investigate the provenance of vanillin. In this study, a variety of commercial vanillin samples and vanilla products were analyzed to provide a frame of reference for the variability of carbon isotope delta values in various vanillin samples, with the results ranging from −20.6 to −36.7‰ relative to the Vienna Peedee Belemnite (VPDB). We present information on the development of two synthetic vanillin reference materials, VANA-1 and VANB-1, prepared in 0.75 g units in glass vials, to be used for the calibration of carbon isotope delta measurements of vanillin and other easily combustible organic materials. Characterization of 40 vials each of VANA-1 and VANB-1 was performed by three laboratories over several measurement sequences. The certified carbon isotope delta values are −31.30 ± 0.06‰ (VANA-1) and −25.85 ± 0.05‰ (VANB-1). These uncertainties, for the 95% confidence level, include considerations for measurement uncertainty, coherence of the reference materials used for calibration, batch homogeneity, and stability during storage and transportation. The results are traceable to the VPDB through a set of nine reference materials (IAEA-CH-6, USGS65, IAEA-600, NBS22, USGS61, IAEA-603, IAEA-610, IAEA-611, and IAEA-612). For up to date certified values, users should refer to doi.org/10.4224/crm.2022.vana-1 and doi.org/10.4224/crm.2022.vanb-1.

The NEON Daily Isotopic Composition of Environmental Exchanges Dataset

The National Ecological Observatory Network (NEON) provides open-access measurements of stable isotope ratios in atmospheric water vapor (δ2H, δ18O) and carbon dioxide (δ13C) at different tower heights, as well as aggregated biweekly precipitation samples (δ2H, δ18O) across the United States. These measurements were used to create the NEON Daily Isotopic Composition of Environmental Exchanges (NEON-DICEE) dataset estimating precipitation (P; δ2H, δ18O), evapotranspiration (ET; δ2H, δ18O), and net ecosystem exchange (NEE; δ13C) isotope ratios. Statistically downscaled precipitation datasets were generated to be consistent with the estimated covariance between isotope ratios and precipitation amounts at daily time scales. Isotope ratios in ET and NEE fluxes were estimated using a mixing-model approach with calibrated NEON tower measurements. NEON-DICEE is publicly available on HydroShare and can be reproduced or modified to fit user specific applications or include additional NEON data records as they become available. The NEON-DICEE dataset can facilitate understanding of terrestrial ecosystem processes through their incorporation into environmental investigations that require daily δ2H, δ18O, and δ13C flux data.

Mercury speciation in Scottish raptors reveals high proportions of inorganic mercury in Scottish golden eagles (Aquila chrysaetos): Potential occurrence of mercury selenide nanoparticles

Knowledge of the uptake and fate of mercury (Hg) compounds in biota is important in understanding the global cycling of Hg and its transfer pathways through food chains. In this study, we analysed total mercury (T-Hg) and methylmercury (MeHg) concentrations in 117 livers of Scottish birds of prey that were found across Scotland and submitted for post-mortem examination through the Raptor Health Scotland project between 2009 and 2019. Statistical comparisons focussed on six species (barn owl, Tyto alba; Eurasian common buzzard, Buteo buteo; golden eagle, Aquila chrysaetos; hen harrier, Circus cyaneus; Eurasian sparrowhawk, Accipiter nisus; and tawny owl, Strix aluco) and showed that golden eagles had a statistically lower fraction of MeHg compared to other raptor species. Further investigation using stable carbon and stable nitrogen isotope ratio measurements carried out for the golden eagles (n = 15) indicated that the increased presence of inorganic mercury (iHg) correlated with a marine influence on the primarily terrestrial diet. Additional bioimaging (n = 1) with laser ablation – inductively coupled plasma – mass spectrometry indicated the co-location of Hg and selenium (Se) within the liver tissue and transmission electron microscopy showed evidence of nanoparticles within the range of 10–20 nm. Further analysis using single particle – inductively coupled plasma – mass spectrometry (n = 4) confirmed the presence of Hg nanoparticles. Together, the evidence suggests the presence of mercury selenide (HgSe) nanoparticles in the liver of some golden eagles that, to our knowledge, has never been directly observed in terrestrial birds of prey. This study points to two alternative hypotheses: these golden eagles may be efficient at breaking down MeHg and form HgSe nanoparticles as a detoxification mechanism (as previously observed in cetaceans), or some golden eagles with elevated iHg may have accumulated these nanoparticles by foraging on stranded cetaceans or seabirds.

An assessment of hydrogen sulfide intrusion in the seagrass Halodule wrightii

Abstract Hydrogen sulfide (H2S, “sulfide”) is a naturally occurring component of the marine sediment. Eutrophication of coastal waters, however, can lead to an excess of sulfide production that can prove toxic to seagrasses. We used stable sulfur isotope ratio (δ34S) measurements to assess sulfide intrusion in the seagrass Halodule wrightii, a semi-tropical species found throughout the Gulf of Mexico, Caribbean Sea, and both western and eastern Atlantic coasts. We found a gradient in δ34S values (−5.58 ± 0.54‰+13.58 ± 0.30‰) from roots to leaves, in accordance with prior observations and those from other species. The results may also represent the first values reported for H. wrightii rhizome tissue. The presence of sulfide-derived sulfur in varying proportions (15–55%) among leaf, rhizome, and root tissues suggests H. wrightii is able to assimilate sedimentary H2S into non-toxic forms that constitute a significant portion of the plant’s total sulfur content.

High precision analysis of stable potassium (K) isotopes by the collision cell MC-ICP-MS “Sapphire” and a correction method for concentration mismatch

A robust correction method is developed to significantly improve stable potassium isotope ratio measurement on a “Sapphire” collision-cell MC-ICP-MS.

Improved protocols for Zn purification and MC-ICP-MS analyses enable determination of small-scale Zn isotope variations

In this study we show that following a newly proposed protocol for stable Zn isotope ratio measurements on a ThermoFisher Scientific Neptune Plus MC-ICP-MS significantly improves the long-term external reproducibility down to < ± 0.025‰ 2SD on δ66/64ZnJMC-Lyon for a single static analysis with 90 measurement cycles of 4.2 s integration time each. This protocol includes: (i) stable isotope measurements in medium-mass resolution mode (R > 6500) to prevent the influence of any polyatomic interferences; (ii) the use of a double-spike, which in our case was a previously designed 64Zn-67Zn mixture; (iii) Zn purification with a two-column anion exchange method; (iv) thorough pre-run sample Zn purity checks and signal matching between sample and reference standard solutions; and, (v) pre-run adjustment of sample carrier and desolvating nebulizer system (DNS) gas flows such that the oxide formation rate determined on the 140Ce16O+/140Ce+ ratio remains below 1%. Following these routines, we obtain long-term external reproducibilities of 0.290 ± 0.017‰ 2SD for the IRMM-3702 (n = 145) certified Zn isotope amount reference material (RM) and − 9.974 ± 0.025‰ 2SD for the Alfa Aesar (n = 75) in-house Zn standard solution. The averages of sets of five single measurements of the IRMM-3702 RM and the Alfa Aesar standard solution narrow down the external reproducibility to ± 0.006‰ and ± 0.023‰ (both given as two standard deviations; for pooled data referred to as 2SD*), respectively. Alternatively, five-fold numbers of measurement cycles can reach the same external reproducibility for single measurements. The δ66/64ZnJMC-Lyon compositions of certified natural rock reference materials obtained by means of individual digests and analyses accurately reproduce the literature values, but our data also show that different batches of the BHVO-2 can be isotopically heterogeneous and clearly affect the reproducibility (BIR-1a: 0.247 ± 0.023‰, n = 17; BCR-2: 0.268 ± 0.025‰, n = 12; BHVO-2 #3323: 0.323 ± 0.024‰, n = 6; BHVO-2 #0535: 0.353 ± 0.015, n = 5, all 2SD). In cases where no effect of heterogeneity on reproducibility could be determined, we report the lowest uncertainty for replicate RM digests combined with multiple measurements (JB-2: 0.225 ± 0.012‰ 2SD, n = 3, i = 15). Mixtures between solution digests of the BIR-1a and BHVO-2 in combination with data pooling of five single measurements indeed demonstrate a measurement accuracy of < ± 0.010‰ 2SD*, emphasizing the analytical capability of the proposed method to depict small-scale Zn isotope variations. With the overall analytical improvement, we seek a better discrimination between variable, and potentially overlapping processes causing Zn isotope fractionation in various terrestrial reservoirs.

Analytical protocols for Phobos regolith samples returned by the Martian Moons eXploration (MMX) mission

Japan Aerospace Exploration Agency (JAXA) will launch a spacecraft in 2024 for a sample return mission from Phobos (Martian Moons eXploration: MMX). Touchdown operations are planned to be performed twice at different landing sites on the Phobos surface to collect > 10 g of the Phobos surface materials with coring and pneumatic sampling systems on board. The Sample Analysis Working Team (SAWT) of MMX is now designing analytical protocols of the returned Phobos samples to shed light on the origin of the Martian moons as well as the evolution of the Mars–moon system. Observations of petrology and mineralogy, and measurements of bulk chemical compositions and stable isotopic ratios of, e.g., O, Cr, Ti, and Zn can provide crucial information about the origin of Phobos. If Phobos is a captured asteroid composed of primitive chondritic materials, as inferred from its reflectance spectra, geochemical data including the nature of organic matter as well as bulk H and N isotopic compositions characterize the volatile materials in the samples and constrain the type of the captured asteroid. Cosmogenic and solar wind components, most pronounced in noble gas isotopic compositions, can reveal surface processes on Phobos. Long- and short-lived radionuclide chronometry such as 53Mn–53Cr and 87Rb–87Sr systematics can date pivotal events like impacts, thermal metamorphism, and aqueous alteration on Phobos. It should be noted that the Phobos regolith is expected to contain a small amount of materials delivered from Mars, which may be physically and chemically different from any Martian meteorites in our collection and thus are particularly precious. The analysis plan will be designed to detect such Martian materials, if any, from the returned samples dominated by the endogenous Phobos materials in curation procedures at JAXA before they are processed for further analyses.

On the Use of Stable Hydrogen Isotope Measurements (δ2H) to Discern Trophic Level in Avian Terrestrial Food Webs

The measurement of stable hydrogen isotope ratios (δ2H) in animal tissues is a popular means of inferring spatial origins and migratory connections. However, the use of this isotope to infer diet and potentially trophic position remains poorly understood, especially in non-aquatic terrestrial ecosystems. In many animal communities, tissue δ15N values are strongly associated with trophic position. Correlations between tissue δ2H and δ15N are expected, then, if δ2H is affected by trophic enrichment of 2H. In addition, within sites, we would expect higher tissue δ2H values in insectivorous species compared to granivores or nectarivores. We tested these hypotheses for two resident avian communities in Nigeria consisting of 30 species representing a range of dietary guilds (granivores, frugivores, nectarivores, omnivores, insectivores) by comparing feather δ2H, δ15N and δ13C values. We found considerable isotopic overlap among all guilds except granivores, with no clear pattern of enrichment in 2H with trophic position. However, at one of our sites (open scrubland), feather δ2H was positively correlated with feather δ15N (R2 = 0.30) compared to a closed canopy forest site (R2 = 0.09). Our results indicate weak evidence for predictable trophic enrichment in 2H in terrestrial environments and indicate that controlled studies are now required to definitively elucidate the behavior of H isotopes in terrestrial food webs.

Chemometric Discrimination of the Geographical Origin of Three Greek Cultivars of Olive Oils by Stable Isotope Ratio Analysis.

Α stable isotope ratio mass spectrometer was used for stable isotope ratio (i.e., δ13C, δ18O, and δ2H) measurements, achieving geographical discrimination using orthogonal projections to latent structures discriminant analysis. A total of 100 Greek monovarietal olive oil samples from three different olive cultivars (cv. Koroneiki, cv. Lianolia Kerkyras, and cv. Maurolia), derived from Central Greece and Peloponnese, were collected during the 2019–2020 harvest year aiming to investigate the effect of botanical and geographical origin on their discrimination through isotopic data. The selection of these samples was made from traditionally olive-growing areas in which no significant research has been done so far. Samples were discriminated mainly by olive cultivar and, partially, by geographical origin, which is congruent with other authors. Based on this model, correct recognition of 93.75% in the training samples and correct prediction of 100% in the test set were achieved. The overall correct classification of the model was 91%. The predictability based on the externally validated method of discrimination was good (Q2 (cum) = 0.681) and illustrated that δ18O and δ2H were the most important isotope markers for the discrimination of olive oil samples. The authenticity of olive oil based on the examined olive varieties can be determined using this technique.