Isotope Research Articles

New Catalysts for Chemical Isotope Exchange between Water and Carbon Dioxide

New Catalysts for Chemical Isotope Exchange between Water and Carbon Dioxide

Chemical and Boron Isotope Characteristics of Snow in the Qiyi Glacier, Qinghai-Tibet Plateau

Snow is a valuable carrier for recording atmospheric information and snowmelt constitutes a crucial hydrological resource for ecosystem sustainability and human activities. The agriculture, industry, livelihoods and ecological security in the Hexi Corridor are dependent on the support of glacier snowmelt in Qilian Mountains of Qinghai-Tibet Plateau. We investigated the main water-soluble ions, trace elements and boron isotopes composition of snow at different altitudes in the Qiyi Glacier of the Qilian Mountains from 12 to 23, Aug. 2020. It is found that Ca2+ and Cl- as the major ions contribute up to 17.08% and 22.42% of the whole ions, respectively. The average Zn concentration exceeds 10 μg/L, as the dominant heavy mental element. Water-soluble ions are mainly influenced by natural sources (salt lakes, deserts), while heavy metal elements are mainly affected by anthropogenic sources like mining activities and the discharge from industrial and agricultural production. The δ11B concentration in the Qiyi Glacier ranges from +13.47 to +22.71 ‰, with an average of +18.40‰, and it is much lower than the average marine δ11B value (+39.5‰). The contribution rate of δ11B in sea salt to dissolved boron (Bsea-salt) in Qiyi Glacier snowfall is only 0.52∼1.77%. The lower mean δ11 B value and Bsea-salt shows that B in the Qiyi Glacier snow is mainly derived from the salt lake in the Qaidam Basin. These results can extend boron isotope research field of the Qinghai-Tibet Plateau and effectively enhance cognition of glacial snow chemistry, particularly in the context of local atmospheric environmental management and ecological construction.

Source term estimation using noble gas and aerosol samples

Algorithms that estimate the location, time, and magnitude of a point-source atmospheric release using remotely sampled air concentrations typically use data for a single chemical or radioactive isotope. A Bayesian algorithm is presented that uses data from multiple radioactive isotopes that are all released in the same short-duration event. Data from noble gas and aerosol samplers can be used simultaneously in the model. Application to a large synthetic data set using four isotopes shows the new algorithm generally gives more accurate location and time estimates than a comparable model using a single isotope.

Breunnerite grain and magnesium isotope chemistry reveal cation partitioning during aqueous alteration of asteroid Ryugu

Returned samples from the carbonaceous asteroid (162173) Ryugu provide pristine information on the original aqueous alteration history of the Solar System. Secondary precipitates, such as carbonates and phyllosilicates, reveal elemental partitioning of the major component ions linked to the primordial brine composition of the asteroid. Here, we report on the elemental partitioning and Mg isotopic composition (25Mg/24Mg) of breunnerite [(Mg, Fe, Mn)CO3] from the Ryugu C0002 sample and the A0106 and C0107 aggregates by sequential leaching extraction of salts, exchangeable ions, carbonates, and silicates. Breunnerite was the sample most enriched in light Mg isotopes, and the 25Mg/24Mg value of the fluid had shifted lower by ~0.38‰ than the initial value (set to 0‰) before dolomite precipitation. As a simple model, the Mg2+ first precipitated in phyllosilicates, followed by dolomite precipitation, at which time ~76−87% of Mg2+ had been removed from the primordial brine. A minor amount of phyllosilicate precipitation continued after dolomite precipitation. The element composition profiles of the latest solution that interacted with the cation exchange pool of Ryugu were predominantly Na-rich. Na+ acts as a bulk electrolyte and contributes to the stabilization of the negative surface charge of phyllosilicates and organic matter on Ryugu.

Chemical Isotope Labeling and Dual-Filtering Strategy for Comprehensive Profiling of Urinary Glucuronide Conjugates.

Glucuronidation, a crucial process in phase II metabolism, plays a vital role in the detoxification and elimination of endogenous substances and xenobiotics. A comprehensive and confident profiling of glucuronate-conjugated metabolites is imperative to understanding their roles in physiological and pathological processes. In this study, a chemical isotope labeling and dual-filtering strategy was developed for global profiling of glucuronide metabolites in biological samples. N,N-Dimethyl ethylenediamine (DMED-d0) and its deuterated counterpart DMED-d6 were used to label carboxylic acids through an amidation reaction. First, carboxyl-containing compounds were extracted based on a characteristic mass difference (Δm/z, 6.037 Da) observed in MS between light- and heavy-labeled metabolites (filter I). Subsequently, within the pool of carboxyl-containing compounds, glucuronides were identified using two pairs of diagnostic ions (m/z 247.1294/253.1665 and 229.1188/235.1559 for DMED-d0/DMED-d6-labeled glucuronides) originating from the fragmentation of the derivatized glucuronic acid group in MS/MS (filter II). Compared with non-derivatization, DEMD labeling significantly enhanced the detection sensitivity of glucuronides, as evidenced by a 3- to 55-fold decrease in limits of detection for representative standards. The strategy was applied to profiling glucuronide metabolites in urine samples from colorectal cancer (CRC) patients. A total of 685 features were screened as potential glucuronides, among which 181 were annotated, mainly including glucuronides derived from lipids, organic oxygen, and phenylpropanoids. Enzymatic biosynthesis was employed to accurately identify unknown glucuronides without standards, demonstrating the reliability of the dual-filtering strategy. Our strategy exhibits great potential for profiling the glucuronide metabolome with high coverage and confidence to reveal changes in CRC and other diseases.

Towards Improved Measurement of Chemical Composition and Isotope Ratios of Rare-earth Phosphates in Atom Probe Tomography

Towards Improved Measurement of Chemical Composition and Isotope Ratios of Rare-earth Phosphates in Atom Probe Tomography

Applications of zinc stable isotope analysis in environmental and biological systems: a review

Zinc (Zn) is an essential trace element that is involved in both biotic and abiotic processes in Earth's surface environments. Over the last 20 years, advances in mass spectrometry instrumentation have enabled unprecedented high-precision Zn isotope abundance ratio determinations in natural and anthropogenic samples. Supported by a solid theoretical background inherited from the traditional non-metal stable isotopes (C, N, H, O, S), the understanding of the controlling factors of Zn isotope fractionation has rapidly evolved. In this article, we review the main applications and findings of Zn isotopes in a variety of scientific domains, including metal contamination, magmatic differentiation, plant uptake, weathering, global climate change, dietary and trophic chains, and biomedicine. The analytical aspects of Zn isotope determination in solid and water samples and the principles and mechanisms of Zn isotope fractionation are also reviewed. This work aims to provide a general yet in-depth panorama of Zn isotope chemistry and to demonstrate the versatility and potential of this isotope system for studying the biological, geological and chemical cycling of Zn.

Study on the Chemical Composition and Lead Isotope Ratios of Lead Glaze Used on Blue Tiles from Gyeoungbokgung Palace

Study on the Chemical Composition and Lead Isotope Ratios of Lead Glaze Used on Blue Tiles from Gyeoungbokgung Palace

Carbon Isotope Chemistry in Protoplanetary Disks: Effects of C/O Ratios

Carbon isotope fractionation of CO has been reported in the disk around TW Hya, where elemental carbon is more abundant than elemental oxygen ([C/O]elem > 1). We investigated the effects of the [C/O]elem ratio on carbon fractionation using astrochemical models that incorporate isotope-selective photodissociation and isotope exchange reactions. The 12CO/13CO ratio could be lower than the elemental carbon isotope ratio due to isotope exchange reactions when the [C/O]elem ratio exceeds unity. The observed 12CO/13CO and H12CN/H13CN ratios around TW Hya could be reproduced when the [C/O]elem ratio is 2–5. In the vicinity of the lower boundary of the warm molecular layer, the formation of ices leads to the gas-phase [C/O]elem ratio approaching unity, irrespective of the total (gas + ice) [C/O]elem ratio. This phenomenon reduces the variation in the 12CO/13CO ratio across different [C/O]elem ratios.

The nucleosynthetic fingerprint of the outermost protoplanetary disk and early Solar System dynamics.

Knowledge of the nucleosynthetic isotope composition of the outermost protoplanetary disk is critical to understand the formation and early dynamical evolution of the Solar System. We report the discovery of outer disk material preserved in a pristine meteorite based on its chemical composition, organic-rich petrology, and 15N-rich, deuterium-rich, and 16O-poor isotope signatures. We infer that this outer disk material originated in the comet-forming region. The nucleosynthetic Fe, Mg, Si, and Cr compositions of this material reveal that, contrary to current belief, the isotope signature of the comet-forming region is ubiquitous among outer Solar System bodies, possibly reflecting an important planetary building block in the outer Solar System. This nucleosynthetic component represents fresh material added to the outer disk by late accretion streamers connected to the ambient molecular cloud. Our results show that most Solar System carbonaceous asteroids accreted material from the comet-forming region, a signature lacking in the terrestrial planet region.

Quantification of gut microbiome metabolites using chemical isotope derivatization strategy combined with LC-MS/MS: Application in neonatal hypoxic-ischemic encephalopathy rat model

The gut microbiome plays pivotal roles in various physiological and pathological processes, with key metabolites including short chain fatty acids (SCFAs), bile acids (BAs), and tryptophan (TRP) derivatives gaining significant attention for their diverse physiological roles. However, quantifying these metabolites presents challenges due to structural similarity, low abundance, and inherent technical limitations in traditional detection methods. In this study, we developed a precise and sensitive liquid chromatography-tandem mass spectrometry (LC-MS/MS) method utilizing a chemical isotope derivatization technique employing 4-(aminomethyl)-N,N-dimethylaniline-d0/d6 (4-AND-d0/d6) reagents to quantify 37 typical gut microbiome-derived metabolites. This method achieved an impressive 1500-fold enhancement in sensitivity for detecting metabolites, compared to methods using non-derivatized, intact molecules. Moreover, the quantitative accuracy of our chemical isotope derivatization strategy proved comparable to the stable isotope labeled internal standards (SIL-IS) method. Subsequently, we successfully applied this newly developed method to quantify target metabolites in plasma, brain, and fecal samples obtained from a neonatal hypoxic-ischemic encephalopathy (HIE) rat model. The aim was to identify crucial metabolites associated with the progression of HIE. Overall, our sensitive and reliable quantification method holds promise in elucidating the role of gut microbiome metabolites in the pathogenesis of various diseases.

Unrecognized extensive charge of microbial gas in the Junggar basin

Different from the Qaidam basin with about 320 billion m3 microbial gas, only limited microbial gases were found from the Junggar basin with similarly abundant type III kerogen. To determine whether microbial gases have not yet identified, natural gas samples from the Carboniferous to Cretaceous in the Junggar basin have been analyzed for chemical and stable isotope compositions. The results reveal some of the gases from the Mahu sag, Zhongguai, Luliang and Wu-Xia areas in the basin may have mixed with microbial gas leading to straight ethane to butane trends with a “dogleg” light methane in the Chung’s plot. Primary microbial gas from degradation of immature sedimentary organic matter is found to occur in the Mahu sag and secondary microbial gas from biodegradation of oils and propane occurred in the Zhongguai, Luliang and Beisantai areas where the associated oils were biodegraded to produce calcites with δ13C values from + 22.10‰ to + 22.16‰ or propane was biodegraded leading to its 13C enrichment. Microbial CH4 in the Mahu sag is most likely to have migrated up from the Lower Wuerhe Formation coal-bearing strata by the end of the Triassic, and secondary microbial gas in Zhongguai and Beisantan uplifts may have generated after the reservoirs were uplifted during the period of the Middle and Late Jurassic. This study suggests widespread distribution of microbial gas and shows the potential to find large microbial gas accumulation in the basin.

Lipopolysaccharide-induced alterations in the liver metabolome of St. Croix and Suffolk sheep

The development of resistance in parasites due to overuse of anthelmintics has resulted in a marked decrease in the efficacy of these drug classes. Recent research efforts have focused on exploring alternatives such as selection for parasite-resistant breeds with the implication that immunocompetence may align with parasite resistance. Two breeds that are often investigated are the St. Croix (STC), a resistant hair breed, and Suffolk (SUF), a susceptible wool breed sheep. The liver plays a vital role in metabolism in the body and metabolizes lipopolysaccharide (LPS), which triggers whole body response through the production of appropriate metabolites, cytokines and immune cells. The objective of this study was to investigate the breed differences in liver metabolome of sheep, with divergent resistance to parasites, in response to LPS. Both STC and SUF sheep (n = 9/breed) were challenged with LPS intravenously. Rectal temperatures and sheep grimace score (SGS) were recorded hourly, for each animal, and averaged across the study for both breeds. The average rectal temperature throughout the study was similar for STC and SUF sheep (40.4°C and 40.2°C respectively), but the pattern of response was different. STC had an average SGS of 0.8 while SUF had an average of 3.3. Liver biopsies were collected from 3 sheep that were not challenged with LPS (HR0; n = 3/breed), two hours post-challenge (HR2; n = 3/breed), and six hours post-challenge (HR6; n = 3/breed). Liver tissue samples were subjected to quantitative untargeted metabolome analysis using chemical isotope labeling/liquid chromatography-mass spectrometry. Pathway analysis of the HR0 metabolome data revealed that 8 pathways (and their associated metabolites) including beta-alanine metabolism, arginine and proline metabolism and glutathione metabolism were altered (false discovery rate-adjusted P-value (FDR) ≤ 0.05) between STC and SUF sheep. At HR2, 10 altered pathways such as folate biosynthesis, taurine and hypotaurine metabolism, and glutathione metabolism. At HR6, only 2 pathways (glycerophospholipid metabolism and purine metabolism) were altered (FDR ≤ 0.05) between STC and SUF sheep. Results highlight the differences in hepatic metabolome and physiological response to LPS challenge that exist between SUF and STC. These findings suggest breed-specific differences in metabolic response to immune challenge, potentially influencing the divergent resistance of the two breeds to parasitic infections.

Salivary metabolomic identification of biomarker candidates for oral melanoma and oral squamous cell carcinoma in dogs.

Oral melanoma (OM) and oral squamous cell carcinoma (OSCC) are frequently diagnosed in dogs, presenting a challenge in distinguishing them from benign oral tumors (BN). Salivary metabolomic biomarkers offer a practical solution because of saliva's direct contact with tumors and the noninvasive nature of collection. Assess the diversity and abundance of the salivary metabolome in dogs with BN, OM, and OSCC using amine/phenol submetabolome analysis and high-performance chemical isotope labeling liquid chromatography-mass spectrometry (CIL LC-MS). Study included 11 BN, 24 OM, 10 OSCC, and 20 healthy control dogs. Case-control cross-sectional study was conducted to assess salivary submetabolic profiles in dogs with BN, OM, and OSCC and healthy dogs. Samples were labeled with 12C-dansyl chloride and analyzed using CIL LC-MS targeted to amine- and phenol-containing metabolites for amine/phenol submetabolome analysis. Distinct clusters and significant differences in metabolite concentrations were observed among the oral cancer, BN, and control groups. A total of 154 and 66 metabolites showed significantly altered concentrations, particularly in OM and OSCC, respectively, when compared with BN (Padj < .05). Potential metabolic biomarkers were identified for each cancer, including decreased concentrations of seryl-arginine and sarcosine in OSCC. Moreover, high-confidence putative metabolites were identified, including an increase in tryptophyl-threonine and a decrease in 1,2-dihydroxynapthalene-6-sulfonic acid and hydroxyprolyl-hydroxyproline for OM. We identified high coverage of the amine/phenol submetabolome, including seryl-arginine, and sarcosine, in OSCC. Our findings emphasize the potential of these biomarkers for distinguishing between oral OSCC and BN in dogs.

Sampling Earth’s mantle at intra-transform spreading ridges

The Doldrums transform system, located in the Equatorial Atlantic at 7–8°N, is a 110 km-wide multi-fault shear zone, with five active transform faults separated by four short intra-transform ridge segments (ITRs). The two central ITRs, ITR-2 and ITR-3, are significantly deeper than the peripheral ridge segments, suggesting differences in the thermal conditions of the sub-ridge mantle. New chemical and radiogenic isotope data from on-axis lavas erupted across the transform domain reveal that the basalts from ITR-3 are enriched in alkalis (Na2O + K2O = 4.3 wt%; Na8 up to 3.7) and light rare earth elements (La/Sm)N = 0.86–0.97). However, these basalts have lower Sr and Pb isotope ratios than MORB from the Equatorial Atlantic (i.e., 87Sr/86Sr ∼ 0.70237 and 206Pb/204Pb ∼ 18), and relatively high Nd and Hf isotope ratios (143Nd/144Nd = 0.51315–0.51325; 176Hf/177Hf = 0.2832–0.28325). Hence, the mantle underlying ITR-3 is, on average, depleted in highly incompatible elements. Thermal models of the sub-ridge mantle show that it is also the coldest mantle region under the Doldrums system with the lowest crust production. Considering its location in the central transform domain, it is likely that the local mantle underwent melting beneath adjacent segments of the Mid-Atlantic Ridge (MAR) before remelting below ITR-3. We propose that the initial melting event beneath the MAR selectively removed the most fusible, geochemically enriched mantle components, leaving behind a predominantly peridotitic source, characterized by comparatively low Sr and Pb isotope ratios. Therefore, MORB from intra-transform ridge segments, such as those within the Doldrums transform system, provide a rare opportunity to constrain the isotopic composition of highly incompatible element depleted peridotitic mantle, which is a ubiquitous, but otherwise often camouflaged component of Earth’s mantle.

Characterizing the stable oxygen isotopic composition of the southeast Indian Ocean

New seawater stable oxygen isotope (δ18O) samples were collected from the southeast Indian Ocean as part of the Coring to Reconstruct Ocean Circulation and Carbon dioxide Across 2 Seas (CROCCA-2S) expedition in November – December of 2018. These data fill a gap in the δ18O sampling coverage of the southern Indian basin, providing new insights into the hydrologic and oceanographic processes influencing the δ18O distribution of the region and its relationship to salinity in the upper ocean. Our surface ocean data (<100 m)—in combination with decades of observations from the broader south Indian Ocean—show distinct δ18O – salinity characteristics on either side of ∼85°E. The balance between evaporation and precipitation yields a strong, robust δ18O – salinity relationship west of 85°E (δ18O = 0.50(±0.01) * S – 17.2(±0.22)). However, within the mesoscale eddy field initiated by the Leeuwin Current further east (∼85–120°E), our observations fall along a mixing line between the southwest Indian Ocean and data collected from the Australian coastal margin, illustrating for the first time how the unique eastern boundary system of the south Indian Ocean drives regional-scale variability in the δ18O – salinity relationship of the surface ocean. A comparison between our observations in the shallow subsurface (100–1000 m) and those from neighboring surveys reinforces this upper ocean connection across the Indo-Australian basin. Antarctic Intermediate Water from the Indian Ocean can be isotopically distinguished from the more regional Tasman Intermediate Water occupying the South Australian Bight, suggesting exchange between the two regions is most prevalent at surface and mode water depths. In deeper waters (> ∼1500 m), we observe a notable 0.87‰ spread in δ18O. This variability may represent interactions between distinct deep water masses in the region, although additional data are needed to confirm. Overall, our data provide a new look at the hydrography and isotopic chemistry of the southeast Indian Ocean, emphasizing the impact of the region's mesoscale eddy field and its interconnectivity with neighboring basins.

Hygroscopic Properties of Plateau Surface Salts: Insights from Chemical Composition and Isotope Signatures

Hygroscopic Properties of Plateau Surface Salts: Insights from Chemical Composition and Isotope Signatures

Deciphering Aphanomyces euteiches-pea-biocontrol bacterium interactions through untargeted metabolomics

Aphanomyces euteiches causes root rot in pea, leading to significant yield losses. However, the metabolites involved in this pathosystem have not been thoroughly studied. This study aimed to fill this gap and explore mechanisms of bacterial suppression of A. euteiches via untargeted metabolomics using pea grown in a controlled environment. Chemical isotope labeling (CIL), followed by liquid chromatography-mass spectrometry (LC–MS), was used for metabolite separation and detection. Univariate and multivariate analyses showed clear separation of metabolites from pathogen-treated pea roots and roots from other treatments. A three-tier approach positively or putatively identified 5249 peak pairs or metabolites. Of these, 403 were positively identified in tier 1; 940 were putatively identified with high confidence in tier 2. There were substantial changes in amino acid pool, and fatty acid and phenylpropanoid pathway products. More metabolites, including salicylic and jasmonic acids, were upregulated than downregulated in A. euteiches-infected roots. 1-aminocyclopropane-1-carboxylic acid and 12-oxophytodienoic acid were upregulated in A. euteiches + bacterium-treated roots compared to A. euteiches-infected roots. A great number of metabolites were up- or down-regulated in response to A. euteiches infection compared with the control and A. euteiches + bacterium-treated plants. The results of this study could facilitate improved disease management.

Source attribution of carbonaceous fraction of particulate matter in the urban atmosphere based on chemical and carbon isotope composition

Air quality is of large concern in the city of Krakow, southern Poland. A comprehensive study was launched by us in which two PM fractions (PM1 and PM10) were sampled during 1-year campaign, lasting from April 21, 2018 to March 19, 2019. A suite of modern analytical methods was used to characterize the chemical composition of the collected samples. The contents of 14 sugars, sugar alcohols and anhydrosugars, 16 polycyclic aromatic hydrocarbons, selected metals and non-metals and ions were analyzed, in addition to organic and elemental carbon content. The carbon isotope composition in both analysed PM fractions, combined with an isotope-mass balance method, allowed to distinguish three main components of carbonaceous emissions in the city: (1) emissions related to combustion of hard coal, (2) emissions related to road transport, and (3) biogenic emissions. The heating season emissions from coal combustion had the biggest contribution to the reservoir of carbonaceous aerosols in the PM10 fraction (44%) and, together with the biogenic emission, they were the biggest contributors to the PM1 fraction (41% and 44%, respectively). In the non-heating season, the dominant source of carbon in PM10 and PM1 fraction were the biogenic emissions (48 and 54%, respectively).

Unraveling Island Economies through Organic Residue Analysis: The Case of Mocha Island (Southern Chile)

Abstract Biophysical conditions played a fundamental role in early human colonization of insular territories, particularly in food-producing societies dealing with limited resources and the challenges of maintaining a sustainable carrying capacity. Studies on past human colonization of small oceanic islands thus offer insights into economic plasticity, ecological impacts, and adaptation of early food-producing groups. On the coast of southern Chile, early evidence is dated to 950 cal BP of island colonization by coastal populations with mainland subsistence systems based on the exploitation of marine resources, along with gathering, managing, and cultivating plants and hunting terrestrial animals. Strikingly, the extent to which these mixed economies contributed to insular colonization efforts is largely unknown. Here we used organic residue analysis of ceramic artifacts to shed light on the subsistence of populations on Mocha Island in southern Chile. We extracted and analyzed lipids from 51 pottery sherds associated with the El Vergel cultural complex that flourished in southern Chile between 950 and 400 cal BP. Chemical and stable isotope analysis of the extracts identified a range of food products, including C3 and C4 plants and marine organisms. The results reveal the central role of mixed subsistence systems in fueling the colonization of Mocha Island.