Deuterium Isotope Research Articles

Hydrochemical Characterisation of the Basement Aquifer with a Focus on the Origin of Nitrate in the Highly Urbanised Niamey Region, SW of Niger

This study investigated the basement aquifer beneath the urbanised city of Niamey and the agricultural fields of Kollo, SW of Niger. During the observation period spanning from 2021 to 2023, groundwater and surface water samples were collected for analysis of major ions and the stable isotopes oxygen-18 and deuterium (δ18O and δ2H) of water. To trace the origin of high nitrate concentrations (NO3−) found in several observation and drinking water wells in both areas, δ15N and δ18O isotope values of NO3− were analysed in groundwater and eluted soil samples. The observed hydrochemical patterns mainly reflect the heterogeneity of the weathered fringe of the basement aquifer. Decreasing concentrations of NO3− and δ18O and δ2H values were observed in relation to the distance of the Niger River and increasing thickness of the clay layer on the surface. The wells close to the river in Niamey show a dilution effect during the flood season, and the NO3− concentrations displayed a continuous increasing trend. The δ15N-NO3 and δ18O-NO3 values confirmed that septic tank water is spreading in the region of Niamey and that manure originating from livestock in Kollo is the main source of NO3−. The patterns of δ15N in the soil samples coincide with those of cattle’s manure spread in both areas. The shallow wells show significantly higher values of electric conductivity and NO3− concentrations compared to the deeper wells, which clearly indicates the influence of shallow septic tanks on water quality.

Achieving a 35-Plex Tandem Mass Tag Reagent Set through Deuterium Incorporation.

Mass spectrometry-based sample multiplexing with isobaric tags permits the development of high-throughput and precise quantitative biological assays with proteome-wide coverage and minimal missing values. Here, we nearly doubled the multiplexing capability of the TMTpro reagent set to a 35-plex through the incorporation of one deuterium isotope into the reporter group. Substituting deuterium frequently results in suboptimal peak coelution, which can compromise the accuracy of reporter ion-based quantification. To counteract the deuterium effect on quantitation, we implemented a strategy that necessitated the segregation of nondeuterium and deuterium-containing channels into distinct subplexes during normalization procedures, with reassembly through a common bridge channel. This multiplexing strategy of "design independent sub-plexes but acquire together" (DISAT) was used to compare protein expression differences between human cell lines and in a cysteine-profiling (i.e., chemoproteomics) experiment to identify compounds binding to cysteine-113 of Pin1.

Construction of Ni−Re Supported on Hydrotalcite‐Derived MgAl Catalysts for Promoting the Ring Hydrogenation of Furfural into Tetrahydrofurfuryl Alcohol in Water

AbstractBiomass‐derived feedstocks play a vital role in sustainable economies for renewable energy, waste management, energy security, and commercial prospects. This study focused on promoting the ring hydrogenation of furfural (FAL) into tetrahydrofurfuryl alcohol (THFA) in an aqueous solution using a potential Ni−Re‐supported hydrotalcite‐derived MgAl catalyst at different Ni : Re molar ratios. Structural analyses, such as an in situ time‐resolved X‐ray absorption near edge structure, under H2 reduction elucidated the simultaneous transformation of Re6+ and Re7+ to Re0 with the remaining highly stable Ni2+. The construction of Ni−Re on hydrotalcite‐derived MgAl catalyst resulted in the alleviated H2 reduction behavior, facilitated H2 adsorption and desorption processes, and suitable catalyst acidity detected by H2 temperature‐programmed reduction, and H2 and NH3 temperature‐programmed desorption experiments, respectively. Under optimized conditions, a maximum THFA yield of 78 % with a complete FAL conversion was attained using Ni1Re0.16/MgO−Al2O3 catalyst at a reaction temperature of 140 °C, H2 pressure of 20 bar, catalyst loading of 20 %, and reaction time of 2 h in a H2O system. Isotopic deuterium (D2O) labeling revealed that D substitution was notably pronounced through isotopic exchange between the D atom from D2O and H atom in FAL during its hydrogenation to THFA.

Groundwater Dynamics in African Endorheic Basins in Arid to Semi-Arid Transition Zones: The Batha Aquifer System, NE Chad

This study investigates the Batha endorheic basin in Chad, situated east of the Lake Chad basin in the arid to semi-arid Sahelian zone. This region has not yet undergone comprehensive geological and hydrogeological studies. More broadly, the transition zone between semi-arid and arid climates has been minimally explored. This research aims to evaluate the resources and dynamics of this multi-layered system using a combined geology-hydrogeology-hydrochemistry-isotopes approach. The multilayer system includes sedimentary layers (Quaternary, Pliocene, and Eocene) over a crystalline basement. A piezometric investigation of the system shows a general SE–NW groundwater, indicating an interconnection between all layers. Hydrochemical analyses identifies four main facies (calcium-bicarbonate, sodium-bicarbonate, sulphate-sodium, and mixed), primarily controlled by water–rock interaction with secondary influences from base-exchange and evaporation. Saturation indices indicate that these waters are close to equilibrium with the calcite-Mg phases, gaylussite and gypsum. Stable isotopes (oxygen-18 and deuterium) categorize groundwater into three groups: ancient water, recent and older meteoric water mixtures affected by evaporation, and mixtures more heavily impacted by evaporation. Tritium contents reveal three groups: current rainwater, modern water, and sub-modern water. These results indicate that ionic and isotopic differentiations cannot be strictly linked to specific layers, confirming the interconnected nature of the Batha system. The observed heterogeneity is mainly influenced by lithological and climatic variations. This study, though still limited, enhances significantly the understanding of the basin’s functioning and supports the rational exploitation of its vital resources for the Batha area’s development. Future investigations to complete the present study are highlighted.

Identification of biological signatures of cruciferous vegetable consumption utilizing machine learning-based global untargeted stable isotope traced metabolomics.

In recent years there has been increased interest in identifying biological signatures of food consumption for use as biomarkers. Traditional metabolomics-based biomarker discovery approaches rely on multivariate statistics which cannot differentiate between host- and food-derived compounds, thus novel approaches to biomarker discovery are required to advance the field. To this aim, we have developed a new method that combines global untargeted stable isotope traced metabolomics and a machine learning approach to identify biological signatures of cruciferous vegetable consumption. Participants consumed a single serving of broccoli (n = 16), alfalfa sprouts (n = 16) or collard greens (n = 26) which contained either control unlabeled metabolites, or that were grown in the presence of deuterium-labeled water to intrinsically label metabolites. Mass spectrometry analysis indicated 133 metabolites in broccoli sprouts and 139 metabolites in the alfalfa sprouts were labeled with deuterium isotopes. Urine and plasma were collected and analyzed using untargeted metabolomics on an AB SCIEX TripleTOF 5,600 mass spectrometer. Global untargeted stable isotope tracing was completed using openly available software and a novel random forest machine learning based classifier. Among participants who consumed labeled broccoli sprouts or collard greens, 13 deuterium-incorporated metabolomic features were detected in urine representing 8 urine metabolites. Plasma was analyzed among collard green consumers and 11 labeled features were detected representing 5 plasma metabolites. These deuterium-labeled metabolites represent potential biological signatures of cruciferous vegetables consumption. Isoleucine, indole-3-acetic acid-N-O-glucuronide, dihydrosinapic acid were annotated as labeled compounds but other labeled metabolites could not be annotated. This work presents a novel framework for identifying biological signatures of food consumption for biomarker discovery. Additionally, this work presents novel applications of metabolomics and machine learning in the life sciences.

Assignments of vibrational lines to OD-impurity complexes for adventitious impurities in β-Ga2O3

Hydrogen in β-Ga2O3 passivates shallow impurities and deep-level defects and can have a strong effect on conductivity. More than a dozen O–D vibrational lines have been reported for β-Ga2O3 treated with the heavy isotope of hydrogen, deuterium. To explain the large number of O–D centers that have been observed, the involvement of additional nearby defects and impurities has been proposed. A few O–H centers have been associated with specific impurities that were introduced intentionally during crystal growth. However, definitive assignments of O–H and O–D vibrational lines associated with important adventitious impurities, such as Si and Fe, have been difficult. A set of well-characterized Si-doped β-Ga2O3 epitaxial layers with different layer thicknesses has been deuterated and investigated by vibrational spectroscopy to provide new evidence for the assignment of a line at 2577 cm−1 to an OD–Si complex. The vibrational properties of several of the reported OD-impurity complexes are consistent with the existence of a family of defects with a VGa1ic−D center at their core that is perturbed by a nearby impurity.

Constructing Ni-Pt Bimetallic Catalysts for Catalytic Hydrogenation and Rearrangement of Furfural into Cyclopentanone with Insight in H/D Exchange by D2O Labeling.

Developing a metallic catalyst for converting furfural (FAL) to highly valuable products such as cyclopentanone (CPO) is important for fine chemical synthesis by the efficient utilization of biomass resources. The presence of diverse unsaturated carbon atoms in FAL and the rearrangement of oxygen atoms hinder the production of CPO. We developed an optimal nickel (Ni)-to-platinum (Pt) molar ratio (1:0.007) for a bimetallic Ni-Pt/alumina (Al2O3) catalyst with a low Pt loading via an impregnation method to efficiently catalyze the selective hydrogenation of FAL in an aqueous solution to form CPO. The comprehensive characterizations by X-ray diffraction and X-ray absorption near edge structure analyses elucidated the formation of Ni0/Pt0 and Ni2+/Pt4+ after reduction by H2. The addition of a low amount of the Pt-Ni/Al2O3 catalyst resulted in an alleviation of H2 reduction behavior detected by hydrogen temperature-programmed reduction, accompanied by low H2 desorption ability observed by hydrogen temperature-programmed desorption. The catalytic activity of Ni-Pt/Al2O3 was higher than those of Ni/Al2O3 and Pt/Al2O3 catalysts. The maximum CPO yield was 66% with 93% FAL conversion under the optimized conditions (160 °C, 20 bar of H2 pressure, and 2 h). Isotopic deuterium oxide (D2O) labeling revealed the transfer of deuterium (D) atoms from D2O to the intermediates and products during hydrogenation and rearrangement, which confirmed that water was a medium for rearrangement and the source of hydrogen for the reaction. This study developed an efficient catalyst for the catalytic hydrogenation and ring rearrangement of FAL into CPO.

Investigation of hydrogen permeation through niobium membranes in contact with liquid lithium

In fusion devices, liquid lithium is increasingly employed as a plasma-facing material owing to high heat loads and neutron irradiation, as well as the necessity for impurity control in the plasma. Notably, addressing the retention of hydrogen and its isotopes deuterium and tritium is crucial for effective utilization of liquid lithium. To measure and control the hydrogen and deuterium content in liquid lithium, specialized permeation sensors and permeation extraction devices are essential. Consequently, there is a need for research on the permeation and diffusion of hydrogen in liquid lithium and permeable membranes. This paper introduces a model encompassing hydrogen adsorption, diffusion, and permeation in niobium membranes and liquid lithium. Experimental measurements of hydrogen adsorption in liquid lithium and hydrogen permeation in niobium membranes are presented. The scenarios are simulated using hydrogen transport module developed on COMSOL platform, resulting in a relatively good agreement with the experimental data.

A contribution to the understanding of the origin of the Ginebra Gold District mineralizations, Colombia

Ginebra´s gold mineralization is hosted by the Ginebra Ophiolitic Massif and the Buga Batholith, in the western flank of the Central Cordillera of Colombia. Gold occurs as disseminations, quartz-carbonate stockwork veinlets and quartz lodes with a strong structural control and are composed by small amounts of sulfides, mostly pyrite, with galena, sphalerite and chalcopyrite in at least two different deposition events and related to strong sericite-chlorite-epidote haloes, indicative of near-neutral and reduced fluids. Petrography and Raman spectroscopy allowed to identify two main fluid inclusions assemblages primary to pseudo-secondary in origin, both of them aqueous and CO2-rich, with variable N2. Microthermometric analysis indicates the hydrothermal fluids associated with the gold were low saline (0.75-6.22 wt% NaCl equiv.) and presented a minimum trapping temperature ranging from 237.4 to 301.6°C. Petrography and microthermometric results suggest an isothermal fluid mixing and/or H2S loss as the main mechanisms related to gold bi-sulfide/thio-sulfide complexes destabilization and precipitation. Sulfur isotopes indicates a close to zero range (-8.2-+4.8‰), suggesting a restricted fluid circulation through the magmatic rocks of the Buga Batholith and the Ginebra Ophiolitic Massif. Besides, the oxygen and deuterium isotopes from hydrothermal sericite and chlorite accompanying to gold events, indicates a metamorphic origin for the hydrothermal fluids. 40Ar-39Ar dating of the hydrothermal alteration haloes, from El Retiro and La Esperanza, indicates a late Cretaceous-Paleocene age, between 67 and 65 Ma, contemporaneous with a regional strong dextral transpressive deformation related to subduction to obduction and exotic terrane accretion against the north-western part of the South American Plate. Although the hydrothermal fluid characteristics of the Ginebra Gold Disctrict are compatible with both the Intrusion-Related and Orogenic Gold deposit types, the metamorphic nature of the hydrothermal fluids and the tectonic regime at the time of mineralization event, allow us to propose they are compatible with an Orogenic Gold deposit.

Are lipids always depleted? Comparison of hydrogen, carbon, and nitrogen isotopic values in the muscle and lipid of larval lampreys.

Stable isotope ratios in organisms can be used to estimate dietary source contributions, but lipids must first be accounted for to interpret values meaningfully. Lipids are depleted in heavy isotopes because during lipid synthesis light isotopes of carbon (12C) and hydrogen (1H) are preferentially incorporated. Prior work in larval lampreys has noted unusual lipid effects, which suggest lipids are enriched in the heavy isotope of carbon (13C), but still depleted in the heavy isotope of hydrogen (deuterium; 2H); nitrogen, a relatively rare element in lipids, has not been identified as being as sensitive to lipid content. Our objective was to determine if stable isotope ratios of hydrogen, carbon, and nitrogen behaved as expected in larval lampreys, or if their lipids presented different isotopic behavior. The δ2H, δ13C, and δ15N were measured from the muscle of four lamprey species before and after lipid extraction. In addition, muscle of least brook lamprey (Lampetra aepyptera) was collected every three months for a year from two streams in Maryland. Isotopic ratios were measured in bulk and lipid-extracted muscles, as well as in extracted lipids. The difference between muscle samples before and after lipid extraction (Δδ2H, Δδ13C, Δδ15N) was positively related to lipid proxy (%H or C:N ratio) and were fit best by linear models for Δδ2H and Δδ15N, and by a non-linear model for Δδ13C. The difference between lipid-extracted muscle and lipid δ13C (ΔMLδ13C) was negative and varied between months (ANOVA, F3,53 = 5.05, p < 0.005). Our work suggests that while lipids are often depleted in 13C, this is not a universal rule; however, the depletion of 2H in lipid synthesis appears broadly true.

Spatial and temporal variability of environmental proxies from the top 120 m of two ice cores in Dronning Maud Land (East Antarctica)

Abstract. The Antarctic ice sheet's future contribution to sea level rise is difficult to predict, mostly because of the uncertainty and variability of the surface mass balance (SMB). Ice cores are used to locally (kilometer scale) reconstruct SMB with a very good temporal resolution (up to sub-annual), especially in coastal areas where accumulation rates are high. The number of ice core records has been increasing in recent years, revealing an important spatial variability and different trends of SMB, highlighting the crucial need for greater spatial and temporal representativeness. We present records of density, water stable isotopes (δ18O, δD, and deuterium excess), major ions concentrations (Na+, K+, Mg2+, Ca2+, MSA, Cl−, SO42-, and NO3-), and continuous electrical conductivity measurement (ECM), as well as age models and resulting surface mass balance from the top 120 m of two ice cores (FK17 and TIR18) drilled on two adjacent ice rises located in coastal Dronning Maud Land and dating back to the end of the 18th century. Both environmental proxies and SMB show contrasting behaviors, suggesting strong spatial and temporal variability at the regional scale. In terms of precipitation proxies, both ice cores show a long-term decrease in deuterium excess (d-excess) and a long-term increase in δ18O, although less pronounced. In terms of chemical proxies, the non-sea-salt sulfate (nssSO42-) concentrations of FK17 are twice those of TIR18 and display an increasing trend on the long-term, whereas there is only a small increase after 1950 in TIR18. The SO42-/Na+ ratios show a similar contrast between FK17 and TIR18 and are consistently higher than the seawater ratio, indicating a dominant impact of the nssSO42- on the SO42- signature. The mean long-term SMB is similar for FK17 and TIR18 (0.57 ± 0.05 and 0.56 ± 0.05 mi.e.yr-1, respectively), but the annual records are very different: since the 1950s, TIR18 shows a continuous decrease while FK17 has shown an increasing trend until 1995 followed by a recent decrease. The datasets presented here offer numerous development possibilities for the interpretation of the different paleo-profiles and for addressing the mechanisms behind the spatial and temporal variability observed at the regional scale (tens of kilometers) in East Antarctica. The “Mass2Ant IceCores” datasets are available on Zenodo (https://doi.org/10.5281/zenodo.7848435; Wauthy et al., 2023).

Heavy water inhibits DNA double-strand break repairs and disturbs cellular transcription, presumably via quantum-level mechanisms of kinetic isotope effects on hydrolytic enzyme reactions.

Heavy water, containing the heavy hydrogen isotope, is toxic to cells, although the underlying mechanism remains incompletely understood. In addition, certain enzymatic proton transfer reactions exhibit kinetic isotope effects attributed to hydrogen isotopes and their temperature dependencies, indicative of quantum tunneling phenomena. However, the correlation between the biological effects of heavy water and the kinetic isotope effects mediated by hydrogen isotopes remains elusive. In this study, we elucidated the kinetic isotope effects arising from hydrogen isotopes of water and their temperature dependencies in vitro, focusing on deacetylation, DNA cleavage, and protein cleavage, which are crucial enzymatic reactions mediated by hydrolysis. Intriguingly, the intracellular isotope effects of heavy water, related to the in vitro kinetic isotope effects, significantly impeded multiple DNA double-strand break repair mechanisms crucial for cell survival. Additionally, heavy water exposure enhanced histone acetylation and associated transcriptional activation in cells, consistent with the in vitro kinetic isotope effects observed in histone deacetylation reactions. Moreover, as observed for the in vitro kinetic isotope effects, the cytotoxic effect on cell proliferation induced by heavy water exhibited temperature-dependency. These findings reveal the substantial impact of heavy water-induced isotope effects on cellular functions governed by hydrolytic enzymatic reactions, potentially mediated by quantum-level mechanisms underlying kinetic isotope effects.

ВЗАЄМОДІЯ Н(D,Т)О З МІНЕРАЛЬНИМИ АДСОРБЕНТАМИ У СТАЦІОНАРНИХ СИСТЕМАХ

Background. The theoretical basis of the experiments is the idea that the significant adsorption properties of layered silicates of the montmorillonite and palygorskite groups and clinoptilolite with a developed specific surface due to the dynamic nature of adsorption-desorption processes due to kinetic isotope effects can ensure priority retention of mineral particles of more inert hydroxide groups ОТ– near the adsorption surfaces. Methods. Cherkasy bentonite with a montmorillonite content of 75 % (hereafter montmorillonite), Varvarivska saponite, and Sokyrnytsky clinoptilolite were used for the experiments. Experiments were performed in stationary mode in hermetically sealed containers (two-phase watermineral system). Results. During the first 7 days of interaction of the aqueous and mineral phases, the specific activity of tritium in the working solution decreased by 31.8–69.5 %. Subsequently, during the 92 days of interaction of the aqueous solution of H(D,T)O with mineral adsorbents, the change in the specific activity of tritium did not exceed 2–4 %. At the same time, the initial concentration of deuterium in the working solution of Н(D,Т)О of two-phase water-mineral systems decreased by only 0.8–14 %, ranging from 0.0066 % to 0.0408 %. During the experiment, in closed water-mineral systems, a partial interphase redistribution of the initial stock of hydrogen isotopes, which was accumulated in the initial working solution Н(D,Т)О, took place. In the process of adsorption of the solution by mineral adsorbents, the initial moisture in the mineral phase was replaced by Н(D,Т)О and the content of hydrogen isotopes increased in them. The content of tritium in the adsorbate, depending on the mineral type of the adsorbent, increased by 31.8 to 69.5 %. Concentration of deuterium increased by 10.1–48.6 %, which was due to the different adsorption capacity of mineral adsorbents. Adsorption of the H(D,T)O working solution by mineral adsorbents was accompanied by fractionation of heavy hydrogen isotopes. Сonclusions. Аs a result of the interaction of the Н(D,Т)О solution with mineral adsorbents, kinetic isotope effects determined the priority retention of more inert hydroxide ОТ-groups than OD- groups near the adsorption surface of mineral particles. Consequently, interphase fractionation of heavy hydrogen isotopes occurred in stationary water-mineral systems. The coefficients of tritium interphase fractionation range from α = 1.26 for palyhorskite to α = 2.96 for clinoptilolite. For deuterium, this indicator is equal to α = 0.89 for clinoptilolite and to α = 1.10 for saponite.

Improved Measurements of Muonic Helium Ground-State Hyperfine Structure at a Near-Zero Magnetic Field.

Muonic helium atom hyperfine structure (HFS) measurements are a sensitive tool to test the three-body atomic system and bound-state quantum electrodynamics theory, and determine fundamental constants of the negative muon magnetic moment and mass. The world's most intense pulsed negative muon beam at the Muon Science Facility of the Japan Proton Accelerator Research Complex allows improvement of previous measurements and testing further CPT invariance by comparing the magnetic moments and masses of positive and negative muons (second-generation leptons). We report new ground-state HFS measurements of muonic helium-4 atoms at a near-zero magnetic field, performed for the first time using a small admixture of CH_{4} as an electron donor to form neutral muonic helium atoms efficiently. Our analysis gives Δν=4464.980(20) MHz (4.5ppm), which is more precise than both previous measurements at weak and high fields. The muonium ground-state HFS was also measured under the same conditions to investigate the isotopic effect on the frequency shift due to the gas density dependence in He with CH_{4} admixture and compared with previous studies. Muonium and muonic helium can be regarded as light and heavy hydrogen isotopes with an isotopic mass ratio of 36. No isotopic effect was observed within the current experimental precision.

Interpretable Machine Learning and Reactomics Assisted Isotopically Labeled FT-ICR-MS for Exploring the Reactivity and Transformation of Natural Organic Matter during Ultraviolet Photolysis.

Isotopically labeled FT-ICR-MS combined with multiple post-analyses, including interpretable machine learning (IML) and a paired mass distance (PMD) network, was employed to unravel the reactivity and transformation of natural organic matter (NOM) during ultraviolet (UV) irradiation. FT-ICR-MS analysis was used to assign formulas, which were classified on the basis of their molecular compositions and structural categories. Isotope (deuterium, D) labeling was utilized to unequivocally determine the photochemical products and examine the development of OD radical-mediated NOM transformation. With regard to the reactive molecular formulas, CHOS formulas exhibited the highest reactivity (86.5% of precursors disappeared) followed by CHON (53.4%) and CHO (24.6%) formulas. With regard to structural categories, the degree of reactivity decreased in the following order: tannins > condensed aromatics > lignin/CRAMs. The IML algorithm demonstrated that the crucial features governing the reactivity of formulas were the molecular weight, DBE-O, NOSC, and the presence of heteroatoms (i.e., N and S), suggesting that the large and unsaturated compounds containing S and N are more prone to photodegradation. The reactomics approach using the PMD network further indicated that 11 specific molecular formulas in the CHOS and CHO class served as hubs, implying a higher photoreactivity and participation in a range of transformations. The isotope labeling analyses also found that, among the reactions observed, hydroxylation (i.e., +OD) is dominant for lignin/CRAMs and condensed aromatics, and formulas containing ≤10 D atoms were developed. Overall, this study, by adopting rigorous and interpretable techniques, could provide in-depth insights into the molecular-level dynamics of NOM under UV irradiation.

Ultralight Ultrafast Enzymes.

Inorganic materials depleted of heavy stable isotopes are known to deviate strongly in some physicochemical properties from their isotopically natural counterparts. Here we explored for the first time the effect of simultaneous depletion of the heavy carbon, hydrogen, oxygen and nitrogen isotopes on the bacterium E. coli and the enzymes expressed in it. Bacteria showed faster growth, with most proteins exhibiting higher thermal stability, while for recombinant enzymes expressed in depleted media, faster kinetics was discovered. At room temperature, luciferase, thioredoxin and dihydrofolate reductase and Pfu DNA polymerase showed up to a 250 % increase in activity compared to the native counterparts, with an additional ∼50 % increase at 10 °C. Diminished conformational and vibrational entropy is hypothesized to be the cause of the accelerated kinetics. Ultralight enzymes may find an application where extreme reaction rates are required.

Ultralight Ultrafast Enzymes**

AbstractInorganic materials depleted of heavy stable isotopes are known to deviate strongly in some physicochemical properties from their isotopically natural counterparts. Here we explored for the first time the effect of simultaneous depletion of the heavy carbon, hydrogen, oxygen and nitrogen isotopes on the bacterium E. coli and the enzymes expressed in it. Bacteria showed faster growth, with most proteins exhibiting higher thermal stability, while for recombinant enzymes expressed in depleted media, faster kinetics was discovered. At room temperature, luciferase, thioredoxin and dihydrofolate reductase and Pfu DNA polymerase showed up to a 250 % increase in activity compared to the native counterparts, with an additional ∼50 % increase at 10 °C. Diminished conformational and vibrational entropy is hypothesized to be the cause of the accelerated kinetics. Ultralight enzymes may find an application where extreme reaction rates are required.

Geological Trap Controlling the Residence Time of Groundwater in Assessment of Exploitation Zone for Its Sustainable Resources Case Study: The Slope of Karang Mount, Banten Province, Indonesia

The southern slope of Mount Karang is covered by complex volcanic deposits with complicated texture and structure. The study on zone or location of water resources which would be exploited required a comprehensive hydrogeological approach. Through detailed geological mapping, spring sampling, and well drilling were carried out. Representative spring water samples were taken to be analyzed in the laboratory, and to obtain the data of physical groundwater, chemical groundwater, stable isotopes 18O (oxygen-18), and deuterium contents, as well as the age of the groundwater. In general, the groundwater facies of the studied area showed Ca, Na, KHCO3 with several sites indicating changes to CaHCO3 during the dry and rainy seasons. The synthesis results of the stable isotope 18O (oxygen-18) and deuterium contents, verified by the physical and chemical groundwater controlled by geological setting in the groundwater subbasins, show the anomaly of residence time as trapped by the normal fault in the middle of the studied area. The existing normal fault might control this anomaly of residence time of groundwater surrounding site JH1, JH9, and JH20. However, the distribution of three different water source zones occurred. All group of groundwater indicated a complex flowing with geological setting controlling the physical, chemical content, and the age of the groundwater. At last, sites JH4, JH5, and JH9 show that the zones are proper to be developed as sustainability groundwater resources. Keywords: groundwater facies, stable isotope, groundwater flow, sustainable water

Electron ionization fragmentation studies for a series of 4-methoxymethylene benzoate esters.

Product ion studies and stable isotope deuterium labeling experiments provide useful data for understanding the electron ionization (EI)-mass spectroscopy (MS) fragmentation of methoxymethylene substituted benzoate esters. The methoxymethylene ether is regioisomeric with the ethoxy group and represents the two possible ether substituents of a benzene ring of C2 H5 O. Structural confirmation of these synthetic precursor materials via gas chromatography (GC)-EI-MS revealed unexpected fragment ions. The synthesis and EI-MS evaluation of some homologs and deuterated derivatives allowed for the characterization of these unique ions and their fragmentation pathways. The relative effects of the position of the oxygen of the ether side chain are the subject of this investigation. The desired compounds were prepared from 4-chloromethylbenzoyl chloride by alkoxide displacement followed by transesterifications and the deuterated analogs were prepared similarly. The compounds were separated by capillary GC and their MS fragmentation evaluated in EI, MS/MS and chemical ionization experiments. The methoxymethylene-substituted benzoate esters yield major fragment ions from the loss of the alkyl group from the ether as well as alkoxy group loss from the ester or ether portion of the molecule. The loss of the alkyl group from the ether followed by loss of the ester alkoxy group as the corresponding alcohol yielded the unique cation at m/z 133 for all compounds. The identity of the major ions was confirmed by product ion and deuterium labeling studies and possible mechanisms of fragment ion formation are described. The aliphatic oxygen of the alkoxymethylene group plays a much more active role in the EI-MS fragment formation profile than the direct aromatic ring linked oxygen of the ethoxy group. Thus, yielding a greater variety of characteristic fragments. The m/z 133 ion is unique to this class of compounds and does not have an equivalent pathway for the regioisomeric ethoxy series.

Recent Progress in Functional Nanomaterials towards the Storage, Separation, and Removal of Tritium.

Tritium is a sustainable next-generation prime fuel for generating nuclear energy through fusion reactions to fulfill the increasing global energy demand. Owing to the scarcity-high demand tradeoff, tritium must be bred inside a fusion reactor to ensure sustainability and must therefore be separated from its isotopes (protium and deuterium) in pure form, stored safely, and supplied on demand. Existing multistage isotope separation technologies exhibit low separation efficiency and require intensive energy inputs and large capital investments. Furthermore, tritium-contaminated heavy water constitutes a major fraction of nuclear waste, and accidents like the one at Fukushima Daiichi leave behind thousands of tons of diluted tritiated water, whose removal is beneficial from an environmental point of view. In this review, the recent progress and main research trends in hydrogen isotope storage and separation by focusing on the use of metal hydride (e.g., intermetallic, and high-entropy alloys), porous (e.g., zeolites and metal organic frameworks (MOFs)), and 2-D layered (e.g., graphene, hexagonal boron nitride (h-BN), and MXenes) materials to separate and store tritium based on their diverse functionalities are discussed. Finally, the challenges and future directions for implementing tritium storage and separation are summarized in the reviewed materials.