Isotope Exchange Research Articles

Application of membrane electrode assembly for water hydrogen isotope exchange

Hydrogen isotope separation will be important for future hydrogen energy applications. The materials used in polymer electrolyte fuel cells (PEFCs), such as the hydrophobic support and Pt catalyst, are essentially the same to those used in the conventional isotope-separation method of water hydrogen chemical exchange. Hereby, deuterium (D) separation was performed with a PEFC. The separation was improved with increasing the water vapor and temperature. D was enriched into the dew water in the cell. The quantities of D conversion from the gas through the vapor to the dew water was measured. The conversion values were less than the simulated ones. This was attributed to the vapor pressure drop and the wetted catalyst surface by the water condensation.

A 2D Ba2N Electride for Transition Metal-Free N2 Dissociation under Mild Conditions.

N2 activation is a key step in the industrial synthesis of ammonia and other high-value-added N-containing chemicals, and typically is heavily reliant on transition metal (TM) sites as active centers to reduce the large activation energy barrier for N2 dissociation. In the present work, we report that a 2D electride of Ba2N with anionic electrons in the interlayer spacings works efficiently for TM-free N2 dissociation under mild conditions. The interlayer electrons significantly boost N2 dissociation with a very small activation energy of 35 kJ mol-1, as confirmed by the N2 isotopic exchange reaction. The reaction of anionic electrons with N2 molecules stabilizes (N2)2- anions, the so-called diazenide, in the large interlayer space (∼4.5 Å) sandwiched by 2 cationic slabs of Ba2N as the main intermediate.

Combined model for 15N, 13C, and spin-state chemistry in molecular clouds

We present a new gas-grain chemical model for the combined isotopic fractionation of carbon and nitrogen in molecular clouds. To this end, we have developed gas-phase and grain-surface chemical networks where the isotope chemistry of carbon and nitrogen is coupled with a time-dependent description of spin-state chemistry, which is important for nitrogen chemistry at low temperatures. We updated the rate coefficients of some isotopic exchange reactions considered previously in the literature, and here we present a set of new exchange reactions involving molecules substituted in 13C and 15N simultaneously. We applied the model to a series of zero-dimensional simulations representing a set of physical conditions across a prototypical prestellar core, exploring the deviations of the isotopic abundance ratios in the various molecules from the elemental isotopic ratios as a function of physical conditions and time. We find that the 12C/13C ratio can deviate from the elemental ratio to a high factor depending on the molecule, and that there are highly time-dependent variations in the ratios. The HCN/H13CN ratio, for example, can obtain values of less than ten depending on the simulation time. The 14N/15N ratios tend to remain close to the assumed elemental ratio within approximately 10%, with no clearly discernible trends for the various species as a function of the physical conditions. Abundance ratios between 13C-containing molecules and 13C+15N-containing molecules however show somewhat increased levels of fractionation as a result of the newly included exchange reactions, though they still remain within a few tens of percent of the elemental 14N/15N ratio. Our results imply the existence of gradients in isotopic abundance ratios across prestellar cores, suggesting that detailed simulations are required to interpret observations of isotopically substituted molecules correctly, especially given that the various isotopic forms of a given molecule do not necessarily trace the same gas layers.

Analysis of Operating Modes of a Countercurrent Column for the Chemical Isotope Exchange between Hydrogen and Water with Independent Flows of Water and Hydrogen

Analysis of Operating Modes of a Countercurrent Column for the Chemical Isotope Exchange between Hydrogen and Water with Independent Flows of Water and Hydrogen

OXYGEN ISOTOPE FRACTIONATION IN THE SILICATE-CARBONATE SYSTEM DURING THE ROCK FORMATION OF THE KOVDOR MASSIF (KOLA PENINSULA)

For the first time the δ18O values both in carbonate and non-carbonate (Ol, Phl, Mt) components of the rocks (calcite carbonatites, phoscorites, ijolites, turyaites) of the Kovdor massif were studied to clarify the role of contamination processes, retrograde exchange, and high-temperature fractionation in the igneous system. It has been established that the processes of crustal contamination are not recorded in the isotopic characteristics of the silicate part of the rocks, and the δ18О values of olivine, phlogopite, and magnetite are lowered compare to the compositions attributed to equilibrium with mantle peridotite. At the same time, the carbonate component of the rocks shows complementary enrichment in the 18O isotope with respect to the composition of derivatives of mantle melts. Estimates of the δ18О closure temperature of the olivine and the rates of rock cooling do not support the hypothesis of retrograde isotopic exchange. A hypothesis is proposed about the presence of a stage of redistribution of oxygen isotopes between the silicate and carbonate components of melts in the magmatic system, which took place before the formation of the Kovdor massif and its cooling. According to oxygen isotope data, the carbonate component could sharply predominate (1.5–4.5 times) over the silicate component during the equilibration.

Proterozoic Deep Carbon—Characterisation, Origin and the Role of Fluids during High-Grade Metamorphism of Graphite (Lofoten–Vesterålen Complex, Norway)

Graphite formation in the deep crust during granulite facies metamorphism is documented in the Proterozoic gneisses of the Lofoten–Vesterålen Complex, northern Norway. Graphite schist is hosted in banded gneisses dominated by orthopyroxene-bearing quartzofeldspathic gneiss, including marble, calcsilicate rocks and amphibolite. The schist has major graphite (<modality 39%), quartz, plagioclase, pyroxenes, biotite (Mg# = 0.67–0.91; Ti < 0.66 a.p.f.u.) and K-feldspar/perthite. Pyroxene is orthopyroxene (En69–74) and/or clinopyroxene (En33–53Fs1–14Wo44–53); graphite occurs in assemblage with metamorphic orthopyroxene. Phase diagram modelling (plagioclase + orthopyroxene (Mg#-ratio = 0.74) + biotite + quartz + rutile + ilmenite + graphite-assemblage) constrains pressure-temperature conditions of 810–835 °C and 0.73–0.77 GPa; Zr-in-rutile thermometry 726–854 °C. COH fluids stabilise graphite and orthopyroxene; the high Mg#-ratio of biotite and pyroxenes, and apatite Cl < 2 a.p.f.u., indicate the importance of fluids during metamorphism. Stable isotopic δ13Cgraphite in the graphite schist is −38 to −17‰; δ13Ccalcite of marbles +3‰ to +10‰. Samples with both graphite and calcite present give lighter values for δ13Ccalcite = −8.7‰ to −9.5‰ and heavier values for δ13Cgraphite = −11.5‰ to −8.9‰. δ18Ocalcite for marble shows lighter values, ranging from −15.4‰ to −7.5‰. We interpret the graphite origin as organic carbon accumulated in sediments, while isotopic exchange between graphite and calcite reflects metamorphic and hydrothermal re-equilibration.

Chloride exchanges between oceanic sediments and seawater: Constraints from chlorine isotopes

We investigate the chlorine isotope disequilibrium between chlorides in pore fluids and chlorides in seawater and infer its consequences for chlorine isotope exchange between ocean sediment pore fluids and seawater. We illustrate our methodology with pore fluids from two IODP drilled to depths of ≈1000 m (U1456 and U1457) in the Indus River fan dominated by clay-detritus sediments of the western Himalayas. At these two sites, the concentrations of chloride and sodium ions do not show significant changes with depth and remain very close to those of seawater. As a function of depth, however, chlorides show a progressive decrease in 37Cl (downto −2.5 and −1.4 ‰ respectively), while Ca2+ increases and Mg2+ decreases, as commonly observed in clay-rich oceanic sediments. The rate of the δ37Cl decrease is correlated to the lithology and sedimentation rate. Examining the chlorine budget on these two sites, we conclude that: (1) Most of the chlorine (≥96% of the total Cl) is contained in the pore fluids as chlorides, while the chlorine stored in the other sinks (minerals or organochlorine) is generally very minor (representing <4% of the total Cl). (2) These other sinks are too small to sequester the lost 37Cl-enriched chlorine, which could compensate for the decreased δ37Cl of the chlorides observed in the pore fluids (assuming that the pore fluids originally had chlorides with the chlorine isotopic composition of seawater, δ37Cl = 0 ‰). (3) This lost 37Cl-enriched chlorine has been released from the sediment into the overlying seawater, with fluxes of about 20 mol of chloride per square metre per kiloyear.In order to evaluate the consequence of this unbalanced on a global scale, we extend this chlorine budget analysis to 22 other oceanic sites drilled by IODP in a variety of tectonic environments. It is estimated that worldwide oceanic sediment pore fluids contain 1 × 1020 mol of chloride with mean δ37Cl at −2.3 ± 0.1 ‰ and mean chlorinity at 0.290 ± 0.055 mol Cl- per kg of sediment. Most of the calculated values of the lost 37Cl-enriched chlorine flux are between 3.5 and 45.6 mol of chloride per square metre per kiloyear (mean value of 18.3 mol Cl.m−2.kyr−1), corresponding to a typical chloride exchange time between sediments and seawater of between 5.5 and 71 Myr with a mean value of 14 Myr. Importantly, in oceanic sediments, a relationship between the δ37Cl of the chlorides in their pore fluids and the nature of the detrital minerals (smectite, illite, kaolinite, carbonate, quartz, …) may exists. This relationship should be modulated by the detrital input from the continents to the oceanic sediments and should therefore be a consequence of the climatic conditions on the continents (mainly rain, temperature). The δ37Cl of the seawater should vary according to these detrital inputs. The expected range of variation would be between −0.3 and +0.3 ‰. This is consistent with the range of δ37Cl in seawater predicted by the study of evaporites deposited since 2 Ga (Eggenkamp et al., 2019).

Mercury Isotope Fractionation during Dark Abiotic Reduction of Hg(II) by Dissolved, Surface-Bound, and Structural Fe(II).

Stable mercury (Hg) isotope ratios are an emerging tracer for biogeochemical transformations in environmental systems, but their application requires knowledge of isotopic enrichment factors for individual processes. We investigated Hg isotope fractionation during dark, abiotic reduction of Hg(II) by dissolved iron(Fe)(II), magnetite, and Fe(II) sorbed to boehmite or goethite by analyzing both the reactants and products of laboratory experiments. For homogeneous reduction of Hg(II) by dissolved Fe(II) in continuously purged reactors, the results followed a Rayleigh distillation model with enrichment factors of -2.20 ± 0.16‰ (ε202Hg) and 0.21 ± 0.02‰ (E199Hg). In closed system experiments, allowing reequilibration, the initial kinetic fractionation was overprinted by isotope exchange and followed a linear equilibrium model with -2.44 ± 0.17‰ (ε202Hg) and 0.34 ± 0.02‰ (E199Hg). Heterogeneous Hg(II) reduction by magnetite caused a smaller isotopic fractionation (-1.38 ± 0.07 and 0.13 ± 0.01‰), whereas the extent of isotopic fractionation of the sorbed Fe(II) experiments was similar to the kinetic homogeneous case. Small mass-independent fractionation of even-mass Hg isotopes with 0.02 ± 0.003‰ (E200Hg) and ≈ -0.02 ± 0.01‰ (E204Hg) was consistent with theoretical predictions for the nuclear volume effect. This study contributes significantly to the database of Hg isotope enrichment factors for specific processes. Our findings show that Hg(II) reduction by dissolved Fe(II) in open systems results in a kinetic MDF with a larger ε compared to other abiotic reduction pathways, and combining MDF with the observed MIF allows the distinction from photochemical or microbial Hg(II) reduction pathways.

Synthesis of 4-(pyrazol-1-yl)pyrimidines from 4-hydrazinopyrimidines and investigation of their structure and some chemical properties

By reacting 2-benzyl-4-hydrazinopyrimidines with ethoxymethylidene derivatives of β-dicarbonyl compounds, the corresponding substituted 4-(1H-pyrazol-1-yl)pyrimidines were synthesized. In a number of examples, intermediates - products of condensation of the reagents in ethanol, were isolated, indicating that the initial attack on the nitrogen atom of the hydrazine fragment involves the ethoxymethylidene group. It was noted that subsequent cyclization of the intermediates in acetic acid leads to 4-(1H-pyrazol-1-yl)pyrimidines. Alkylation of the synthesized non-fused bicyclic systems was carried out and it was proved that the nitrogen atom N-1 of the pyrimidine ring undergoes alkylation. A complex of 2-benzyl-4-(5′-methyl-4′-ethoxycarbonylpyrazol-1′-yl)-6-methylpyrimidine with copper (II) chloride was synthesized. X-ray diffraction analysis proved that, in contrast to the metal complexes of similar pyrazolylpyrimidines, in this case, a single-dentate complex with a linear structure of the composition ligand:metal, 2/1, is formed, and the nitrogen atom N-1 of the pyrimidine ring participates in the formation of a bond with the metal atom, as well as during alkylation. It was found that H/D exchange occurs in pyrazolylpyrimidine molecules in a solution of CD3ONa in CD3OD. Using the methods of 1H NMR spectroscopy and high-resolution mass spectrometry, it was proved that the hydrogen atoms of the alkyl groups of the studied systems undergo isotope exchange. The kinetics of H/D exchange was studied using some examples. It has been shown that the presence of an allyl group in the pyrimidine ring significantly affects the direction and rate of the H/D exchange. The structure of all synthesized substances was confirmed by NMR methods (1H, 13C, NOESY), high-resolution mass spectrometry and in some examples X-ray diffraction analysis was also performed.

Biosynthesis of UDP-β-l-Arabinofuranoside for the Capsular Polysaccharides of Campylobacter jejuni.

Campylobacter jejuni is the leading cause of food poisoning in North America and Europe. The exterior surface of this bacterium is coated with a capsular polysaccharide (CPS) which enables adherence to the host epithelial cells and evasion of the host immune system. Many strains of C. jejuni can be differentiated from one another by changes in the sequence of the carbohydrates found within the CPS. The CPS structures of serotypes HS:15 and HS:41 of C. jejuni were chemically characterized and found to contain an l-arabinofuranoside moiety in the repeating CPS sequence. Sequence similarity and genome neighborhood networks were used to identify the putative gene cluster within the HS:15 serotype for the biosynthesis of the l-arabinofuranoside fragment. The first enzyme (HS:15.18) in the pathway was found to catalyze the NAD+-dependent oxidation of UDP-α-d-glucose to UDP-α-d-glucuronate, while the second enzyme (HS:15.19) catalyzes the NAD+-dependent decarboxylation of this product to form UDP-α-d-xylose. The UDP-α-d-xylose is then epimerized at C4 by the third enzyme (HS:15.17) to produce UDP-β-l-arabinopyranoside. In the last step, HS:15.16 catalyzes the FADH2-dependent conversion of UDP-β-l-arabinopyranoside into UDP-β-l-arabinofuranoside. The UDP-β-l-arabinopyranoside mutase catalyzed reaction was further interrogated by measurement of a positional isotope exchange reaction within [18O]-UDP-β-l-arabinopyranoside.

Mineralogy and genesis of the Pb-Zn-Sb-Ag vein H32A in the Příbram uranium and base-metal district, Bohemian Massif, Czech Republic

A detailed paragenetic, electron microprobe, fluid inclusion and S,C,O-isotope study was conducted on Pb-Zn-Sb-Ag mineralization of the vein H32A, Háje deposit, Příbram uranium and base-metal district, Czech Republic. The vein is hosted by folded Neo-Proterozoic sandstones and siltstones of the Teplá-Barrandian unit in exo-contact of the Central Bohemian Plutonic Complex of the Variscan age (354–335 Ma). The ore zone is close to a crustal-scale tectonic zone dividing two distinctly different basement blocks of the Bohemian Massif. A rich mineral assemblage consisting of 44 mineral phases formed during two major mineralization stages (siderite-sulphidic and calcite-sulphidic) widespread in the Příbram area. A complex history of the vein is evidenced from the presence of seven mineralization sub-stages and widespread repeated metasomatic replacement and dissolution of older vein during younger mineralizing events. The vein is dominated by carbonates (especially siderite-rhodochrosite, less frequently dolomite-ankerite-kutnohorite, rarely calcite), minor constituents are quartz, illite-muscovite, and chamosite (locally with up to 1.52 apfu Sb, 0.53 apfu Zn and 0.38 apfu Pb). Ore minerals are dominated by Ag-poor galena. The Fe-poor sphalerite, pyrrhotite, löllingite, arsenopyrite, Pb-Sb, Pb-Sb-Ag and Cu-Ag-Sb sulphosalts are subordinate phases and dyscrasite, native antimony and native arsenic are accessories. The fluid inclusion study revealed the wide ranges of homogenization temperatures (210–<100 °C) and salinities (0.0–30.5 wt% NaCl eq.) of exclusively aqueous fluid inclusions. General decrease of both parameters occurred during evolution of the vein. Sulphur isotope disequilibrium was found between co-existing galenas and sphalerites. The calculated fluid δ13C values range between −9.0 and −12.3 ‰ V-PDB, implying for a well-mixed source of carbon, or its significant re-cycling during processes of dissolution-reprecipitation of vein carbonates. The calculated fluid δ18O values are highly positive for early siderite (+7.2 to +9.6 ‰ V-SMOW), and near-zero for later dolomites and calcites (−2.9 to +3.2 ‰ V-SMOW). The siderite fluids likely represent deeply circulated waters, which underwent a significant isotope exchange with hot crustal rocks. Late low-salinity fluids were likely sourced from the Permian partly evaporated freshwater piedmont basins. The high-salinity Ca-Na-Cl brines rarely recorded in secondary fluid inclusions hosted by late calcite likely represent either local “shield brines” or basinal brines of marine provenance. The study site covers a metallogenetically significant portion of the Late Variscan fluid history within an active crust-scale tectonic zone hosted by basement of the Bohemian Massif. A pronounced Ag enrichment of this vein is mainly caused by widespread occurrence of inclusions of late-stage Ag minerals (dyscrasite) in the vein, which form rich concentrations in the shallower parts of the Háje deposit.

Enhancing oxygen exchange kinetics of solid oxide fuel cell cathode: Unleashing the potential of higher order Ruddlesden-Popper phase surface modification

Tailoring the electrode surface represents a promising strategy to enhance electrochemical performance while preserving base material integrity. Achieving appropriate surface coverage with catalytic active oxide material is critical for efficient oxygen transport at the triple phase boundary (TPB). To further explore this approach, the perovskite structure La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) is decorated with a higher order Ruddlesden-Popper phase Pr4Ni3O10+δ (PNO). This combination is being investigated using electrical conductivity relaxation (ECR) technique to study the oxygen exchange kinetics. Samples with varying surface coverage of PNO are examined in a temperature range of 650 °C–850 °C, with a step change in pO2 between 0.1 atm and 0.21 atm. The chemical diffusion coefficient, Dchem, remains invariant across all the samples, however, the surface exchange coefficient, kchem, varies with the surface coverage of PNO. Notably, the coated sample with a PNO loading content of 0.28 mg cm−2, referred to as PNO5, demonstrates a significant enhancement of nearly two orders of magnitude in kchem compared to bare LSCF at 650 °C. This substantial improvement is ascribed to the increased active sites of ORR within the TPB region and the facilitated electron access through tunneling from LSCF to the coated phase. Pulse isotopic exchange (PIE) measurements on the fractionated powders confirm the fast surface exchange kinetics of PNO. Such remarkable oxygen exchange characteristics encourage the use of PNO, along with LSCF, as potential candidates for SOFC cathodes.

Mitigation of the diagenesis risk in biological apatite δ18O interpretation

The assessment of the potential blurring effect of diagenetic processes represents the greatest challenge for geochemists whose purpose is to reconstruct environmental parameters based on isotopic proxies. Numerous studies performed on phosphatic remains from terrestrial and marine sedimentary deposits have shown post-depositional isotopic modifications due to exchange reactions with surrounding waters. If diagenesis may be diagnosed through several lines of evidence such as mineralogical or chemical modifications of the pristine in vivo apatite after burial in soils and sediments, diagenesis does not prove that bioapatite phosphate exchanged oxygen isotopes with aqueous fluids. Therefore, we propose a new method of detection of diagenetic alteration of bioapatite phosphate based on a statistical approach designed to analyze sample collections. The approach requires that phosphatic remains belonged to animals living during a short time interval and within an environment characterized by steady air or water temperature and the δ18O of ambient water. We show that the distribution of bioapatite phosphate δ18O follows a normal distribution resulting from the combination of independent factors such as those related to the genetics, environment and analytical measurements. In the case of oxygen isotope exchange between the bioapatite phosphate and various amounts of circulating aqueous fluids, our numerical simulations reveal that the distributions of bioapatite phosphate δ18O are asymmetric with shapes depending on the temperature of reaction and the composition of the reacting aqueous fluid. This new statistical tool based on mass balance equations and Monte Carlo simulations is considered valuable to mitigate the diagenesis risk in the interpretation of bioapatite phosphate δ18O as paleoecological and paleoclimatic proxies.

B(C6F5)3-Catalyzed Intramolecular Hydroalkoxylation Deuteration Reactions of Unactivated Alkynyl Alcohols.

Using D2O as a deuterium source, a method for the deuteration of intra- and extra-cyclic methylene has been developed for cyclic ethers with moderate yield and excellent deuterium incorporation. This transformation features superb functional group tolerance in a wide range of alkynols. Notably, the critical factor to achieve high deuterium incorporation is determined by the hydrogen isotope exchange reaction of an unstable oxonium ion. This novel methodology provides an efficient and concise synthetic route to a number of valuable deuterated cyclic ethers that are often difficult to prepare with other methods.

Covariation between oxygen and hydrogen stable isotopes declines along the path from xylem water to wood cellulose across an aridity gradient.

Oxygen and hydrogen isotopes of cellulose in plant biology are commonly used to infer environmental conditions, often from time series measurements of tree rings. However, the covariation (or the lack thereof) between δ18 O and δ2 H in plant cellulose is still poorly understood. We compared plant water, and leaf and branch cellulose from dominant tree species across an aridity gradient in Northern Australia, to examine how δ18 O and δ2 H relate to each other and to mean annual precipitation (MAP). We identified a decline in covariation from xylem to leaf water, and onwards from leaf to branch wood cellulose. Covariation in leaf water isotopic enrichment (Δ) was partially preserved in leaf cellulose but not branch wood cellulose. Furthermore, whilst δ2 H was well-correlated between leaf and branch, there was an offset in δ18 O between organs that increased with decreasing MAP. Our findings strongly suggest that postphotosynthetic isotope exchange with water is more apparent for oxygen isotopes, whereas variable kinetic and nonequilibrium isotope effects add complexity to interpreting metabolic-induced δ2 H patterns. Varying oxygen isotope exchange in wood and leaf cellulose must be accounted for when δ18 O is used to reconstruct climatic scenarios. Conversely, comparing δ2 H and δ18 O patterns may reveal environmentally induced shifts in metabolism.

Permeability and diffusion of tritium in bentonite

Abstract. As a part of the Croatian RD&amp;amp;D (research, development, and demonstration) program within the Program for LILW (low- and intermediate-level waste) and SNF (spent nuclear fuel) disposal, research of permeability and the diffusion of tritium in bentonite was organized, as part of the research of the future engineering barriers for repositories of LILW and SNF. Two types of materials were prepared, namely pure sodium bentonite and a mixture of sodium bentonite (12 %) with quartz sand (88 %). Compaction of materials was conducted with a modified Proctor test, and the apparatus was designed and made at the Faculty of Mining, Geology and Petroleum Engineering at the University of Zagreb, utilizing fused deposition modeling 3D printer and PETG (polyethylene terephthalate glycol) material. Water enriched with 3H has been prepared by dilution of the National Institute of Standards and Technology (NIST) 3H standard (4926e) to 6 L. The activity of the prepared enriched water was 49 700±180 TU. One part of the device was filled with 3H-free water and the other with 3H-spiked water (0.6 L volume for each part). In total, five devices with bentonite and five devices with a sand–bentonite mixture were prepared this way. The devices were thoroughly sealed to avoid loss of sample and isotopic exchange with the atmosphere and put horizontally in holders. The water for 3H activity measurements was sampled monthly or bimonthly. A total of 8 mL of the sample was taken by syringe and transferred to a measurement vial. Each vial was additionally filled with 12 mL of a scintillator (Ultima Gold LLT, PerkinElmer) and thoroughly mixed. 3H activity was determined by a liquid scintillation counter (LSC; Quantulus 1220) at the Laboratory for Low-level Radioactivities, Ruđer Bošković Institute, Zagreb. Due to the penetration of bentonite from the barrier into the water samples, tritium-free water has relatively high activity after 2 months of the experiment (average value was 5560±240 TU). In the final sampling, after a 2-month time span, the activity reached 9670±2490 TU. Later, sampling and measurement were not possible due to the high bentonite amount within the samples. Tritium-free samples from the sand–bentonite mixture device were stable, and the first analyses (1 month after the experiment setup) showed an average activity of 533±31 TU, while the final (5-month time span from the first sampling) average activity was 12 800±3430 TU. The increase in the concentration from the beginning to the end of the experiment was almost exponential. Spiked samples from the bentonite device had an average activity of 36 950±2550 TU at the first sampling and 17 580±13 320 TU after a 1-month time leg. Later, sampling was not possible. Spiked samples from sand–bentonite mixture showed a decrease in tritium activity from the first sampling (43 390±1310 TU) to 27 210±285 TU (5 months after the first sampling). Considering the penetration of bentonite material into the water samples, only the sand–bentonite mixture can be considered for further analyses through the calculation of the diffusion.

Oxygen diffusion and surface exchange coefficients measurements under high pressure: Comparative behavior of oxygen deficient versus over‐stoichiometric air electrode materials

AbstractMixed ionic electronic conductors (MIECs) oxides are used as electrode materials for solid oxide cell (SOC) application, as they combine high electronic conductivity as well as high oxygen diffusivity and oxygen surface exchange coefficients. The ionic transport properties can be directly determined thanks to the isotopic exchange depth profiling (IEDP) method. To date, the reported measurements have been performed at ambient pressure and below. However, for a higher efficiency of hydrogen production at the system level, it is envisaged to operate the cell between 10 and 60 bar. To characterize the MIEC oxides properties in such conditions, an innovative setup able to operate up to a total pressure of 50 bar and 900°C has been developed. The main goal of this study was to compare the behavior of two types of reference materials: the oxygen deficient La‐Sr‐Fe‐Co perovskites, and the overstoichiometric lanthanide nickelates Ln2NiO4+δ (Ln = La, Pr, Nd). Diffusion and surface exchange coefficients obtained under 6.3 bar of oxygen are measured and their evolution discussed in light of the change in oxygen stoichiometries. This analysis allows better understanding of the dependency of the surface exchange coefficient with the oxygen partial pressure.

Oxygen Isotopic Fractionation in a Silicate–Carbonate System during the Formation of Rocks of the Kovdor Pluton (Kola Peninsula)

The δ18О values of carbonates and silicates (Ol, Phl, Mt) of calcite carbonatites, phoscorites, ijolites, and turjaites of the Kovdor pluton have been studied for the first time to elucidate the role of processes of contamination, retrograde exchange, and high-temperature fractionation in a magmatic system. It is established that no processes of crustal contamination are registered in the isotopic characteristics of silicates and that the δ18О values of olivine, phlogopite, and magnetite are lower relative to the compositions typical of equilibrium with mantle peridotite. At the same time, the carbonates show a complementary enrichment in the 18О isotope relative to the composition of derivative mantle melts. The estimated closure temperature of the O isotopic composition of olivine and the cooling rates of rocks do not support a hypothesis on retrograde isotope exchange. A redistribution of O isotopes between silicate and carbonate constituents of melts in the magmatic system before the origination of the Kovdor pluton and its cooling is suggested. According to the O isotope data, the carbonate constituent at that moment could strongly be dominant (in 1.5–4.5 times) over the silicate one.

Skeletal metalation of lactams through a carbonyl-to-nickel-exchange logic

Classical metalation reactions such as the metal-halogen exchange have had a transformative impact on organic synthesis owing to their broad applicability in building carbon-carbon bonds from carbon-halogen bonds. Extending the metal-halogen exchange logic to a metal-carbon exchange would enable the direct modification of carbon frameworks with new implications in retrosynthetic analysis. However, such a transformation requires the selective cleavage of highly inert chemical bonds and formation of stable intermediates amenable to further synthetic elaborations, hence its development has remained considerably challenging. Here we introduce a skeletal metalation strategy that allows lactams, a prevalent motif in bioactive molecules, to be readily converted into well-defined, synthetically useful organonickel reagents. The reaction features a selective activation of unstrained amide C–N bonds mediated by an easily prepared Ni(0) reagent, followed by CO deinsertion and dissociation under mild room temperature conditions in a formal carbonyl-to-nickel-exchange process. The underlying principles of this unique reactivity are rationalized by organometallic and computational studies. The skeletal metalation is further applied to a direct CO excision reaction and a carbon isotope exchange reaction of lactams, underscoring the broad potential of metal-carbon exchange logic in organic synthesis.

Hydrogen Exchange and Diffusion Kinetics at Elevated Temperatures in Proton-Conducting Solid Oxide Materials

Storage of purified hydrogen is one of the central challenges in addressing climate change and reducing our reliance on fossil fuels for energy conversion and storage, and therefore there is a global surge in research and development concerning hydrogen purification and storage. In this regard, we are studying proton conduction in solid oxide materials at elevated temperatures for applications in hydrogen separation and compression membranes. Hydrogen compression is the most recommended method to store hydrogen for automotive applications as it allows an increase in the hydrogen volumetric energy density.Traditionally the protonic conductivity in these materials is measured by indirect methods. For example, conductivity measurements in mixed gas atmospheres, comparing for example dry N2 with humidified N2, thereby allowing the contribution of protons to be evaluated. In this study, we for the first time report the evaluation of protonic conductivity in BaZr1-xCexY0.2O3−δ, BaZr0.1Ce0.7Y0.2–xYbxO3–δ and Ba7Nb4MoO20 by direct measurements afforded by the Isotope Exchange Depth Profiling technique with deuterium labelling. We also report the kinetics of H/D transport through the bulk materials and across metal-ceramic interfaces with a particular interest in the behaviour of the interface between the key Pd/Pd alloy catalyst component and the hydrogen-transporting oxide ceramic material. The transport and interface behaviour information will be of significance in designing hydrogen separation and compression membranes. Figure 1