Distribution Of Deuterium Research Articles

Cluster dynamics modeling of hydrogen retention and desorption in tungsten with saturation and multi-trapping effect of sinks

Hydrogen (H) retention and desorption in tungsten (W)-based plasma-facing materials are still not well understood, largely due to the limitations of ex-situ observations in experimental detection methods like thermal desorption spectroscopy (TDS). In order to reveal the fundamental mechanisms behind H retention and desorption, we developed a cluster dynamics model, IRadMat-TDS, for theoretical modeling of depth distribution and TDS of deuterium (D) in polycrystalline W. The model newly includes the saturated absorption and emission of D in inherent sinks like grain boundaries (GBs), as well as the multi-trapping effect of D in various types of GBs with different trapping energies. The simulated TDS spectra are in agreement with experimental ones. For polycrystalline W under D ion irradiation within keV-energy range, two typical thermal desorption peaks in TDS at around 490 and 550 K are explicitly attributed to D emission from GBs and vacancies, respectively. And GBs play a major role in D retention. Moreover, the broad peaks in TDS come from the convolution of multi-trapping of D in sinks with different types of trapping sites rather than a single-site approximation.

The biological impact of deuterium and therapeutic potential of deuterium-depleted water.

Since its discovery by Harold Urey in 1932, deuterium has attracted increased amounts of attention from the scientific community, with many previous works aimed to uncover its biological effects on living organisms. Existing studies indicate that deuterium, as a relatively rare isotope, is indispensable for maintaining normal cellular function, while its enrichment and depletion can affect living systems at multiple levels, including but not limited to molecules, organelles, cells, organs, and organisms. As an important compound of deuterium, deuterium-depleted water (DDW) possess various special effects, including but not limited to altering cellular metabolism and potentially inhibiting the growth of cancer cells, demonstrating anxiolytic-like behavior, enhancing long-term memory in rats, reducing free radical oxidation, regulating lipid metabolism, harmonizing indices related to diabetes and metabolic syndrome, and alleviating toxic effects caused by cadmium, manganese, and other harmful substances, implying its tremendous potential in anticancer, neuroprotective, antiaging, antioxidant, obesity alleviation, diabetes and metabolic syndrome treatment, anti-inflammatory, and detoxification, thereby drawing extensive attention from researchers. This review comprehensively summarizes the latest progress in deuterium acting on living organisms. We start by providing a snapshot of the distribution of deuterium in nature and the tolerance of various organisms to it. Then, we discussed the impact of deuterium excess and deprivation, in the form of deuterium-enriched water (DEW) and deuterium-depleted water (DDW), on living organisms at different levels. Finally, we focused on the potential of DDW as an adjuvant therapeutic agent for various diseases and disorders.

Hydrogen bond symmetrisation in D2O ice observed by neutron diffraction

Hydrogen bond symmetrisation is the phenomenon where a hydrogen atom is located at the centre of a hydrogen bond. Theoretical studies predict that hydrogen bonds in ice VII eventually undergo symmetrisation upon increasing pressure, involving nuclear quantum effect with significant isotope effect and drastic changes in the elastic properties through several intermediate states with varying hydrogen distribution. Despite numerous experimental studies conducted, the location of hydrogen and hence the transition pressures reported up to date remain inconsistent. Here we report the atomic distribution of deuterium in D2O ice using neutron diffraction above 100 GPa and observe the transition from a bimodal to a unimodal distribution of deuterium at around 80 GPa. At the transition pressure, a significant narrowing of the peak widths of 110 is also observed, attributed to the structural relaxation by the change of elastic properties.

In-Electrospray source Hydrogen/Deuterium exchange coupled to multistage fragmentation for the investigation of the protonation and fragmentation pathways of gas phase ions.

Identification of molecules in complex natural matrices relies on matching the fragmentation spectra of ions under investigation and the spectra acquired for the corresponding analytical standards. Currently, there are many databases of experimentally measured tandem mass spectrometry spectra (such as NIST, MzCloud, and Metlin), and considerable progress has been made in the development of software for predicting tandem mass spectrometry fragments in silico using combinatorial, machine learning, and quantum chemistry approaches (such as MetFrag, CFM-ID, and QCxMS). However, the electrospray ionization molecules can be ionized at different sites (protonated or deprotonated), and the fragmentation spectra of such ions are different. Here, we are using the combination of the in-ESI source hydrogen/deuterium exchange reaction and MSn fragmentation for the investigation of the fragmentation pathways for different protomers of organic molecules. It is shown that the distribution of the deuterium in the fragment ions reflects the presence of different protomers. For several molecules, the distribution of deuterium was traced up to the MS5 level of fragmentation revealing many unusual and unexpected effects. For example, we investigated the loss of HF from the ciprofloxacin and norfloxacin ions and observed that for ions protonated at -COOH group, the eliminating hydrogen always comes from -NH group. When ions are protonated at another site, the elimination of hydrogen with a probability of 30% occurs from the -NH group, and with a probability of 70%, it originates from other sites on the molecule. Such effects were not described previously. Quantum chemical simulation was used for the verification of the protonated structures and simulation of the corresponding fragmentation spectra.

Apparatus design of operando hydrogen microscope for visualization of time-dependent distribution of hydrogen

The operando hydrogen microscope is an original apparatus that has been developed to visualize the time-dependent permeation of hydrogen through a sample. This apparatus is developed based on an ultrahigh vacuum scanning electron microscope (UHV SEM). The system consists of a lens system to focus ions produced by electron-stimulated desorption (ESD), an ion detector optimized for ESD-signal detection, and a two-dimensional measurement program synchronized with the position information of the electron beam. The developed detectors and electrostatic lenses enable highly sensitive detection of the ions. In this paper, we show the details of the instrumentation of the operando hydrogen microscope. We have succeeded in recording hydrogen and deuterium flowing from the rear of metals to the surface as a series of time-lapse images, showing the time-dependent changes in the surface distribution of hydrogen and deuterium. Deuterium permeation through the metal sample was dynamically visualized at the surface by the two-dimensional mapping of the desorbed ions induced by scanning electron beam irradiation.

Ligand Control of Copper-Mediated Cycloadditions of Acetylene to Azides: Chemo- and Regio-Selective Formation of Deutero- and Iodo-Substituted 1,2,3-Triazoles.

The participation of σ-monocopper and σ-bis-copper acetylide in mechanistic pathways for copper-catalyzed cycloaddition (CuAAC) reactions of acetylene with azides was probed by analysis of deuterium distributions in the 1,2,3-triazole product formed by deuterolysis of initially formed mono- and bis-copper triazoles. The results show that, when Cu(Phen)(PPh3)2NO3 is used as the catalyst for reactions of acetylene with azides in DMF/D2O, 1-substituted-5-deutero-1,2,3-triazoles are generated selectively. This finding demonstrates that the Cu(Phen)(PPh3)2NO3-catalyzed cycloadditions utilize monocopper acetylide as the substrate and produce 5-copper-1,2,3-triazoles initially. Conversely, when DBU or Et3N is the copper ligand, the process takes place through initial formation and cycloaddition of bis-copper acetylide to produce 4,5-bis-copper-triazole, which reacts with D2O to form the corresponding 4,5-bis-deutero-triazole. Moreover, when C2D2 is used as the substrate, Cu(Phen)(PPh3)2NO3 as the Cu ligand, and H2O/DMF as the solvent, mono-C4-deutreo 1,2,3-triazoles are generated in high yields and excellent levels of regioselectivity. Lastly, CuAAC reactions of acetylene with azides, promoted by CuCl2·2H2O and NaI, yield 4,5-diiodo-1,2,3-triazoles with moderate to high efficiencies.

Characterization of the In Vivo Deuteration of Native Phospholipids by Mass Spectrometry Yields Guidelines for Their Regiospecific Customization.

Customization of deuterated biomolecules is vital for many advanced biological experiments including neutron scattering. However, because it is challenging to control the proportion and regiospecificity of deuterium incorporation in live systems, often only two or three synthetic lipids are mixed together to form simplistic model membranes. This limits the applicability and biological accuracy of the results generated with these synthetic membranes. Despite some limited prior examination of deuterating Escherichia coli lipids in vivo, this approach has not been widely implemented. Here, an extensive mass spectrometry-based profiling of E. coli phospholipid deuteration states with several different growth media was performed, and a computational method to describe deuterium distributions with a one-number summary is introduced. The deuteration states of 36 lipid species were quantitatively profiled in 15 different growth conditions, and tandem mass spectrometry was used to reveal deuterium localization. Regressions were employed to enable the prediction of lipid deuteration for untested conditions. Small-angle neutron scattering was performed on select deuterated lipid samples, which validated the deuteration states calculated from the mass spectral data. Based on these experiments, guidelines for the design of specifically deuterated phospholipids are described. This unlocks even greater capabilities from neutron-based techniques, enabling experiments that were formerly impossible.

Optimizing site-specific specimen preparation for atom probe tomography by using hydrogen for visualizing radiation-induced damage

Atom probe tomography (APT) is extensively used to measure the local chemistry of materials. Site-specific preparation via a focused ion beam (FIB) is routinely implemented to fabricate needle-shaped specimens with an end radius in the range of 50 nm. This preparation route is sometimes supplemented by transmission Kikuchi diffraction (TKD) to facilitate the positioning of a region of interest sufficiently close to the apex. Irradiating the specimen with energetic electrons and ions can lead to the generation of vacancies and even amorphization of the specimen. These extrinsically created vacancies become crucial for probing the hydrogen or deuterium distribution since they act as a strong trap. Here, we investigated the feasibility of site-specific preparation of a two-phase medium-Mn steel containing austenite (fcc) and ferrite (bcc). Following gaseous charging of APT specimens in deuterium (D2), clusters enriched by up to 35 at.% D, are imaged after Pt deposition, conventional Ga-FIB preparation, and TKD conducted separately. These D-rich clusters are assumed to arise from the agglomeration of vacancies acting as strong traps. By systematically eliminating these preparation-induced damages, we finally introduce a workflow allowing for studying intrinsic traps for H/D inherent to the material.

Distribution of hydrogen isotope in the soil around the Qinshan Nuclear Power Plant

When a different types of reactor are operating at the same area and the same period of time, released radionuclides are hard to follow in the environment. In general, isotopic techniques can be used for source localization. To obtain the distribution of hydrogen isotope in soil, eight sampling points were selected along the local dominant wind direction with different distances away from Qinshan Nuclear Power Plant, and soil samples at different depths (0–2, 2–5, 5–10, 10–20, 20–30 cm) were collected in December 2019 and December 2020, respectively. The concentrations of hydrogen isotopes were measured in the soil samples at different depth. The spatial distribution of tritium and deuterium in the surface soil was related to soil properties and the distance from the nuclear power plant. It was found that tritium and deuterium are generally enriched in the upper layer. Determination of the deuterium concentration in the environment may be a new way to trace the released tritium from the reactors.

Tritium distributions in castellated structures of Be limiter tiles from JET-ITER-like wall experiments

Tritium retention in the castellated structure of beryllium limiters used in JET with the ITER-like wall (ILW) during the first (ILW1), third (ILW3) and all three (ILW1-3) campaigns were examined and evaluated. Tritium was deposited on the surfaces inside the castellation grooves together with deuterium, beryllium, oxygen, carbon and small amounts of metallic impurities such as nickel, copper and tungsten. The tritium content after the ILW1 campaign was greater than after the ILW3 campaign. This is attributed to the steadily decreasing amount of carbon impurities in JET from campaign to campaign. The majority of tritium was retained in shallow regions in the grooves, up to 2 mm from the entrance to the gap. It was comparable on all sides of the castellation, i.e. no difference has been detected between the toroidal and poloidal gaps. Secondly, the tritium retention in the gaps was similar on all specimens independent of their position in the tokamak, while the retention on the plasma-facing surfaces clearly depended on the tile position. The tritium deposition patterns in the castellation were also compared with the deuterium distribution determined in earlier studies.

Developments and Challenges in the Design of the ITER DRGA

The ITER Diagnostic Residual Gas Analyzer (DRGA) will measure the distribution of gas species, i.e., deuterium (D), tritium (T), and impurities, in the divertor exhaust stream and in the plasma periphery, with time resolution relevant to fusion plasma–wall particle dynamics. The uniqueness of the DRGA, over previous implementations of plasma dynamics residual gas analysis, is an integrated approach, combining mass and low-temperature plasma-activated optical spectroscopy, in a differentially pumped analysis station. A further unique feature of the ITER divertor-specific DRGA is an ~8-m separation of the analysis station from the sampled pumping duct, while still maintaining a ~1-s response time for hydrogen isotopic concentrations. ITER DRGA final design activities are strongly benefiting from testing of prototypical DRGA components and methods on present fusion devices, most currently on JET and W7-X. DRGA systems are implemented on both these devices and include sensors (and pumping methods) that are directly relevant to the ITER DRGA design. The recent JET-DTE2 campaign has provided the first experience on operating the combined ITER DRGA sensors with D-T plasmas. While enhancing system design for ITER, this experience on operating devices has also revealed additional engineering challenges, which further guide the continuing final design project. Meanwhile, the recent determination that the ITER DRGA, with slight optimization, will resolve the helium isotopes well enough to support an ITER pre-DT, He-3-based heating scheme, has greatly increased ITER Research Program interest in the DRGA and its implementation well ahead of the DT phase.

Effect of initial exposure temperature on the deuterium retention and surface blistering in tungsten

• Exposure temperature in the initial stage strongly affects the subsequent deuterium behavior in tungsten. • Initial exposure at 420 K significantly inhibits the formation of intergranular blisters and leads to a reduction in the size of intragranular blisters. • Initial exposure at a relatively high temperature of 600 K leads to a reduction in the size of intergranular blisters and reduces deuterium retention by ∼ 34 %. • The gradient distribution of deuterium over a larger depth leads to the intergranular cracks more prone to propagate along sloping grain boundaries. Temperature is one of the critical factors that strongly affect the behavior of hydrogen isotopes in tungsten (W). This work investigates the effect of initial exposure temperature on the deuterium (D) retention and surface blistering in recrystallized W. D plasma exposure is started at 420 K and 600 K, respectively, and then changed to the same temperature of 520 K. For each temperature, the irradiation fluence is ∼ 1 × 10 26 D m −2 , and therefore the total fluence is ∼ 2 × 10 26 D m −2 for each sample. A reference W sample was also exposed at 520 K with the same total fluence. Compared with the reference sample, it is found that the initial temperature of 420 K significantly inhibits the formation of intergranular blisters and leads to a reduction of intragranular blisters in size. Although the initial temperature of 600 K facilitates the formation of intergranular blisters, the intergranular blister size is reduced. This is possibly related to the relatively higher concentration of trapped D over a large depth range as revealed by the TMAP simulation results, leading to the fact that intergranular cracks are more prone to propagate along sloping grain boundaries. Thermal desorption spectra results show that the initial exposure temperature of 420 K and 600 K reduce D retention by a factor of ∼ 56 % and ∼ 34 %, respectively. It is considered to be connected with the blistering-induced defects and D transport in W, which are strongly affected by the initial exposure temperature. This work demonstrates that the initial exposure temperature plays a crucial role in D behavior in W, improving the understanding of the temperature effects of hydrogen isotopes behavior in W.

Effects of the energetic particles on the anomalous transport driven by the ion temperature gradient instability

When the charge exchange time (τcx) is sufficiently shorter than the slowing-down time (τsl), the distribution of energetic particles (EPs) is bump-on-tail. In this work, the effects of EPs on the anomalous transport driven by the ion temperature gradient (ITG) instability are investigated. The dispersion relation is theoretically derived and numerically solved to analyze the effects of EPs on the linear frequency of ITG instability. Two kinds of bump-on-tail distribution, denoted by τ=13τsl/τcx=1.133 and 6.8, and the slowing-down distribution, denoted by τ = 0, are considered. Based on the linear results, the quasilinear particle and energy fluxes of bulk ions are analyzed. It is found that effects of the EPs on the ITG linear frequency and quasilinear transport are obvious in the regions with the EPs initial energy E0/Te<60 and the EPs charge concentration Zhεh>0.01, where Te is the electron temperature, Zh and εh are the charge number and fraction of EPs, respectively. Existence of the EPs is beneficial for the stabilization of ITG instability. Moreover, the ITG instability can be better stabilized with the bump-on-tail distribution of energetic deuterium (D) and the slowing-down distribution of energetic helium (He). However, in the cases with the slowing-down distribution of D and the bump-on-tail distribution of He, the particle fluxes of bulk ions are inwardly largest and the energy fluxes of bulk ions are outwardly smallest, which indicate that the better particle and energy confinement appear with the slowing-down distribution of D and the bump-on-tail distribution of He.

Homogeneous Spatial Distribution of Deuterium Chemisorbed on Free-Standing Graphene.

Atomic deuterium (D) adsorption on free-standing nanoporous graphene obtained by ultra-high vacuum D molecular cracking reveals a homogeneous distribution all over the nanoporous graphene sample, as deduced by ultra-high vacuum Raman spectroscopy combined with core-level photoemission spectroscopy. Raman microscopy unveils the presence of bonding distortion, from the signal associated to the planar sp configuration of graphene toward the sp tetrahedral structure of graphane. The establishment of D–C sp hybrid bonds is also clearly determined by high-resolution X-ray photoelectron spectroscopy and spatially correlated to the Auger spectroscopy signal. This work shows that the low-energy molecular cracking of D in an ultra-high vacuum is an efficient strategy for obtaining high-quality semiconducting graphane with homogeneous uptake of deuterium atoms, as confirmed by this combined optical and electronic spectro-microscopy study wholly carried out in ultra-high vacuum conditions.

Hydrogen trapping by irradiation-induced defects in 316 Lstainless steel: A combined experimental and modeling study

The irradiation-induced defects in stainless steel internal components of pressurized water reactors combined with hydrogen uptake during the oxidation process could be a key parameter in the mechanism for Irradiation-Assisted Stress Corrosion Cracking (IASCC). A heat-treated 316 L SS containing a low amount of defects was Fe3+ ions-implanted; irradiation-induced defects types and depth distributions were characterized by Transmission electron microscopy (TEM). Deuterium was then inserted in the specimens either by cathodic charging or by sample exposure to deuterated primary water. Secondary Ions Mass Spectrometry – SIMS – permitted to access the deuterium distribution at the implanted stainless steel surface. A finite difference numerical solver accounting for hydrogen diffusion/trapping coupling was used to simulate the hydrogen transport in the implanted material, taken into consideration the specific heterogeneous character of the irradiation-induced defects distribution in matter. Taking as input data the experimental defects distribution associated with Frank loops or voids, the main trapping sites for hydrogen were assigned to voids, not Frank loops. Such numerical approach was able to deal accurately with the problem of hydrogen transport in a heterogeneous material as well as to differentiate two potential trap sites contributions to the experimental deuterium distribution. In addition, according to results obtained after primary water exposure, trapping at voids was still effective at 320 °C, signature of a high binding energy of hydrogen in voids.

Regularity of Deuteration in Linear Polyethylene Prepared by Saturation of Polycyclopentene over Homogeneous Catalysts

When isotopically labeling polymer chains for small-angle neutron scattering (SANS), it is highly desirable to achieve even intra- and interchain distributions of deuterium (D), such that scatterin...

NanoSIMS analysis of hydrogen and deuterium in metallic alloys: Artefacts and best practice

Hydrogen embrittlement can cause catastrophic failure of high strength alloys, yet determining localised hydrogen in the microstructure is analytically challenging. NanoSIMS is one of the few techniques that can map hydrogen and deuterium in metal samples at microstructurally relevant length scales. Therefore it is essential to understand the artefacts and determine the optimum methodology for its reliable detection. An experimental methodology/protocol for NanoSIMS analysis of deuterium (as a proxy for hydrogen) has been established uncovering unreported artefacts and a new approach is presented to minimise these artefacts in mapping hydrogen and deuterium in alloys. This method was used to map deuterium distributions in electrochemically charged austenitic stainless steel and precipitation hardened nickel-based alloys. Residual deuterium contamination was detected in the analysis chamber as a result of deuterium outgassing from the samples, and the impact of this deuterium contamination was assessed by a series of NanoSIMS experiments. A new analysis protocol was developed that involves mapping deuterium in the passive oxide layer thus mitigating beam damage effects that may prevent the detection of localised deuterium signals when the surface is highly deuterated.

Characterising hydrogen induced cracking of alloy 625+ using correlative SEM - EDX and NanoSIMS

Hydrogen induced cracking behaviour of O&G nickel alloy 625+ (UNS N07716) was investigated. Deuterium was introduced electrochemically into samples by cathodic polarisation (3.5 wt.% NaCl.D2O) under different mechanical conditions. Subsequently, deuterium distributions were mapped using NanoSIMS. Deuterium was used as an isotopic tracer instead of hydrogen to avoid the detection of hydrogen artefacts. Complimentary image analysis using scanning electron microscopy (SEM) and low voltage energy dispersive X-ray (EDX) allowed the identification of microstructural features corresponding to deuterium enrichments. The results provided experimental evidence of enrichments at dislocation slip bands (DSB), twin boundary and grain boundary features that include σ precipitates.

Site-specific specimen preparation for SIMS analysis of radioactive samples.

Secondary Ion Mass Spectrometry is an important technique for the study of the composition of a wide range of materials because of the exceptionally high sensitivity that allows the study of trace elements and the ability to distinguish isotopes that can be used as markers for reactions and transport processes. However, when studying nuclear materials, it is often necessary to analyse highly radioactive samples, and only rather few SIMS facilities are available in active environments. In this paper, we present a methodology using focussed ion beam milling to prepare samples from radioactive specimens that are sufficiently large to undertake SIMS mapping experiments over microstructurally significant regions, but with overall activities small enough to be readily transported and analysed by a SIMS instrument in a normal laboratory environment. Radioactive samples prepared using this methodology can also be used for correlative SIMS analysis with other analytical microscopies. SIMS results showing the distributions of deuterium in oxides on in-reactor corroded zirconium alloys are presented to demonstrate the potential of this sample preparation technique.

LIBS study of ITER relevant tungsten–oxygen coatings exposed to deuterium plasma in Magnum-PSI

We discuss the applicability of laser induced breakdown spectroscopy (LIBS) for deuterium retention analysis in compact and porous tungsten-oxide (W-O) coatings. Deuterium loading was performed by exposing the coatings to deuterium plasma in Magnum-PSI linear plasma device.The deuterium signals obtained by ex-situ LIBS had sufficiently good signal-to-noise ratio for reliable separation of essentially broadened hydrogen and deuterium lines as well as for comparison of the lateral and depth distributions of deuterium in the coatings. Strong deuterium signal was obtained for the first laser shot which corresponded to the surface layer of the W-O coatings whereas deeper in the coating the signal decreased to noise level. In addition, the deuterium signal was highest in the central region of compact W-O coating. For both coatings, depth profiles of elements obtained by LIBS match with those recorded by secondary ion mass spectroscopy (SIMS) in the lateral direction along the sample surface. The results of LIBS and SIMS results were supported by Scanning Electron Microscopy (SEM) and X-ray diffraction (XRD) data which showed that the exposure to deuterium plasma resulted in remarkable changes in the surface morphology along the sample surface. The study demonstrates the LIBS potential in deuterium retention measurements in plasma facing components.