Amount Of Isotope Research Articles

Towards Establishing Best Practice in the Analysis of Hydrogen and Deuterium by Atom Probe Tomography.

As hydrogen is touted as a key player in the decarbonization of modern society, it is critical to enable quantitative hydrogen (H) analysis at high spatial resolution and, if possible, at the atomic scale. H has a known deleterious impact on the mechanical properties (strength, ductility, toughness) of most materials that can hinder their use as part of the infrastructure of a hydrogen-based economy. Enabling H mapping including local hydrogen concentration analyses at specific microstructural features is essential for understanding the multiple ways that H affect the properties of materials including embrittlement mechanisms and their synergies. In addition, spatial mapping and quantification of hydrogen isotopes is essential to accurately predict tritium inventory of future fusion power plants thus ensuring their safe and efficient operation. Atom probe tomography (APT) has the intrinsic capability to detect H and deuterium (D), and in principle the capacity for performing quantitative mapping of H within a material's microstructure. Yet, the accuracy and precision of H analysis by APT remain affected by complex field evaporation behavior and the influence of residual hydrogen from the ultrahigh vacuum chamber that can obscure the signal of H from within the material. The present article reports a summary of discussions at a focused workshop held at the Max-Planck Institute for Sustainable Materials in April 2024. The workshop was organized to pave the way to establishing best practices in reporting APT data for the analysis of H. We first summarize the key aspects of the intricacies of H analysis by APT and then propose a path for better reporting of the relevant data to support interpretation of APT-based H analysis in materials.

A Validated LC-MS/MS Assay for the Quantification of Cholate Isotopes in Human Serum.

Current methods for evaluating liver health rely on nonspecific blood tests, elastography surrogates for fibrosis, and invasive procedures, none of which directly measure liver function and physiology. Herein we present the analytical validation of a unique, highly sensitive LC-MS/MS assay and dual-sample oral (DuO) cholate challenge test to reliably quantify serial serum concentrations of cholate isotopes administered to patients with liver diseases. The clearance of administered cholate isotopes measured by the assay provides information about liver function and physiology. Analytical method validation of the cholate assay analytes (endogenous unlabeled cholic acid, 24-13C-cholic acid, and 2,2,4,4-D4-cholic acid) in terms of accuracy, precision, analytical sensitivity, analytical specificity, and range of reliable response was completed in human serum samples spiked with quality controls and calibrators in accordance with applicable guidelines. DuO test parameters were validated using samples from 48 subjects representing various liver disease etiologies. Accuracy (mean biases) for all analytes ranged from 0.1% to 3.7%. Using a nested components-of-variance design (20 days, 2 runs per day, 2 replicates per sample), total imprecision for all analytes ranged from 2.3% to 8.4%. Lower and upper limits of quantitation were established and validated at 0.1 to 10.0 µM. Matrix effects and potential interferents did not affect assay performance. DuO test validation met all prespecified acceptance criteria. The method validation studies described herein established the performance characteristics in terms of accuracy, precision, analytical sensitivity, analytical specificity, reportable ranges, and reference intervals of the LC-MS/MS cholate assay and DuO test.

Laser Ablation Saturated Absorption Spectroscopy (LA-SAS) for In Situ Detection of Neodymium Isotopes.

This study introduces a novel optical system integrating laser ablation with saturated absorption spectroscopy (LA-SAS) for the detection of neodymium isotopes, crucial for the characterization process in nuclear forensics. Conventional methods for isotope analysis have encountered challenges, such as the inability to perform on-site detection or difficulty in distinguishing minor isotope differences. The LA-SAS system overcomes these limitations by combining pulsed laser for ablation and counter-propagated diode laser for saturated absorption, enabling preparation-free detection with enhanced spectral resolution. The analytical capability was demonstrated through the successful detection of seven neodymium isotopes (142Nd, 143Nd, 144Nd, 145Nd, 146Nd, 148Nd, and 150Nd) with a line width narrowed to 0.1 pm, significantly improving upon the resolution limit of conventional LA-based methods. In addition, quantitative analysis of isotope abundance was facilitated by evaluating the signals from saturated absorption spectra. Special attention was given to the hyperfine structure of odd isotopes, which was resolved by multiple fitting in spectra, thereby refining the accuracy of isotope quantification up to an average bias of 0.45%. The established LA-SAS system offers on-site detection capability based on LA, and also the high resolution from SAS, making it a promising method for in situ nuclear forensics. Consequently, the study enhances the academic understanding of neodymium isotopes and underscores the potential of LA-SAS in fields requiring detailed isotopic information.

Enhancing analytical merits of laser-induced breakdown spectroscopy of hydrogen isotopes using an orthogonal double-pulsing scheme

Accurate detection and quantification of hydrogen isotopes in solid materials are vital for diverse applications, including fusion energy, hydrogen storage, and tritium production. Laser-induced breakdown spectroscopy (LIBS) is a well-established, rapid, standoff method for this purpose, but it faces challenges related to the analytical merits required for isotopic analyses. In this study, we enhance the analytical and detection capabilities of traditional single-pulse LIBS by implementing an orthogonal double pulsing approach, focusing on the analysis of a range of 2H concentrations in Zircaloy-4 substrates (acting as a proxy for 3H). The double-pulse experiments employed an orthogonal re-heating configuration with two nanosecond Nd:YAG lasers. We systematically evaluated critical parameters affecting the signal intensity in double-pulse LIBS, including interpulse delay, ambient gas pressure, and heating laser energy. Our results demonstrate that employing an orthogonal double-pulse scheme significantly enhances 2Hα emission while minimizing line broadening and self-absorption, ultimately improving the technique's analytical capabilities.

Quantification of Hydrogen Isotopes Utilizing Raman Spectroscopy Paired with Chemometric Analysis for Application across Multiple Systems.

Online and real-time analysis of a chemical process is a major analytical challenge that can drastically change the way the chemical industry or chemical research operates. With in situ analyses, a new and powerful understanding of chemistry can be gained; however, building robust tools for long-term monitoring faces many challenges, including compensating for instrument drift, instrument replacement, and sensor or probe replacement. Accounting for these changes by recollecting calibration data and rebuilding quantification models can be costly and time-consuming. Here, methods to overcome these challenges are demonstrated with an application of Raman spectroscopy to monitoring hydrogen isotopes with varied speciation within dynamic gas streams. Specifically, chemical data science tools such as chemometric modeling are leveraged along with several examples of calibration transfer approaches. Furthermore, the optimization of instrument and sensor cell parameters for targeted gas-phase analyses is discussed. While the particular focus on hydrogen is highly beneficial within the nuclear energy sector, mechanisms built and demonstrated here are widely applicable to optical spectroscopy monitoring in numerous other chemical systems that can be leveraged in other processes.

A longitudinal study of endocrinology and foraging ecology of subadult gray whales prior to death based on baleen analysis

Individual-level assessments of wild animal health, vital rates, and foraging ecology are critical for understanding population-wide impacts of exposure to stressors. Large whales face multiple stressors, including, but not limited to, ocean noise, pollution, and ship strikes. Because baleen is a continuously growing keratinized structure, serial extraction, and quantification of hormones and stable isotopes along the length of baleen provide a historical record of whale physiology and foraging ecology. Furthermore, baleen analysis enables the investigation of dead specimens, even decades later, allowing comparisons between historic and modern populations. Here, we examined baleen of five sub-adult gray whales and observed distinct patterns of oscillations in δ15N values along the length of their baleen plates which enabled estimation of baleen growth rates and differentiation of isotopic niche widths of the whales during wintering and summer foraging. In contrast, no regular patterns were apparent in δ13C values. Prolonged elevation of cortisol in four individuals before death indicates that chronic stress may have impacted their health and survival. Triiodothyronine (T3) increased over months in the whales with unknown causes of death, simultaneous with elevations in cortisol, but both hormones remained stable in the one case of acute death attributed to killer whale predation. This parallel elevation of cortisol and T3 challenges the classic understanding of their interaction and might relate to increased energetic demands during exposure to stressors. Reproductive hormone profiles in subadults did not show cyclical trends, suggesting they had not yet reached sexual maturity. This study highlights the potential of baleen analysis to retrospectively assess gray whales' physiological status, exposure to stressors, reproductive status, and foraging ecology in the months or years leading up to their death, which can be a useful tool for conservation diagnostics to mitigate unusual mortality events.

Compensating isotope effect on molecular emission of hydroxyl and imidogen isotopologues in laser-induced plasma

BackgroundThe molecular isotopologues in laser-induced plasma exhibit riddling emission behaviors in terms of wavelength, intensity, and temporal evolution of spectra due to the isotope effect. Although this phenomenon introduces uncertainty to isotope analyses based on molecular spectra, its underlying mechanism remains undisclosed. ResultsIn this study, laser-induced breakdown spectroscopy (LIBS) is employed to identify the emission behavior of hydrogen, oxygen, and nitrogen isotopologues in a plasma plume. The goal is to discern the details of the isotope effect and mitigate resulting uncertainty. The molecular emissions of hydroxyl (OH) and imidogen (NH) were measured from plasma ablated on isotopically enriched water samples. Time-resolved detection clearly reveals distinct isotopic disparities in intensity variation and optimum gate delay, which were attributed to plasma thermo-hydrodynamics. Lighter isotopologues exhibit earlier and faster associations than their heavier counterparts due to their fast reaction rates and expansion velocities. The extent of the isotope effect hinged on plasma characteristics governed by measurement conditions. Consequently, comparing spectral intensity between molecular isotopologues cannot directly indicate the nominal isotope abundance of the sample. To address it, a compensation strategy has been devised, quantifying isotope effects through parameters like the slope and optimum delay of time-resolved detection. The approach successfully predicts nominal isotope abundance using compensated intensity ratios, with an absolute bias of less than 3 %. SignificanceThis study not only offered fundamental insights into the isotope effect in laser-induced plasma but also proposed an alternative method for isotope quantification that circumvents complicated calibration processes.

Influence of lipid extraction in the muscle tissue of the blue crab Callinectes sapidus Rathbun, 1896 (Decapoda: Brachyura: Portunidae) in the determination of δ13C and δ15N

Abstract Stable isotope analysis of δ13C and δ15N has been used in the description of the trophic ecology in marine organisms. This approach has been applied to various taxa including crustaceans. Pre-treatment of samples before isotope quantification is suggested for tissues with high lipid content, because lipids can affect the isotope concentrations. We focused on the isotope analysis of tissues of the blue crab (Callinectes sapidusRathbun, 1896) because it is a significant prey item for intermediate and top predators. We aimed to assess the isotope values produced by two lipid extraction methods and compare these results with values of samples which were not lipid-extracted. Results evidenced a negative relationship between Δδ13C and the C:N ratios, the C:N ratios explaining 98% of the variation in the Δδ13C. Regarding the SEAc results, the δ13C values showed more negative values after the lipid extraction Bligh and Dryer method, which indicates that this method is accurate for pre-treatment of samples before isotope quantification. These results highlighted the importance of lipid extraction before quantifying isotopes and enforces the need of pre-treatment of samples.

Quantification and Tracing of Stable Isotope into Cysteine and Glutathione.

The analysis of metabolic perturbation in biological samples is crucial to understand mechanisms of metabolic diseases. Here, we describe a protocol for quantitative stable isotope-labeled metabolite tracing of cysteine metabolism in cultured cells. This protocol relies on an extraction protocol to derivatize free thiols to prevent oxidation. In addition, the quantitative tracing of serine into multiple pathways, including the glutathione synthesis pathway, allows for the interrogation of cysteine and glutathione synthesis. This protocol provides a flexible framework that can be adapted to interrogate many metabolites and pathways of interest.

A Practical Procedure for Analysis of Lead Isotopes in Bivalve Shells Using Laser Ablation Multicollector Inductively Coupled Plasma Mass Spectrometry (LA-MC-ICP-MS).

Lead, like other trace elements, is incorporated in the growing bands of bivalve shells. The chemicals stored into the shells can provide valuable information about seawater conditions during the period of shell formation. In this study, we present a practical approach to determine Pb isotopic signatures in bivalve shells as a tool for evaluating lead pollution in coastal waters. To demonstrate the applicability of the method, Pb isotopic fingerprinting in bivalve shell layers were investigated using laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS). Lead isotope ratios (208Pb/206Pb and 206Pb/207Pb) were measured along distinct sections of the maximum growth axis of the shells. Calibration and quantification of Pb isotopes were performed using NIST 612 as reference material. Our results demonstrated that Pb isotope ratios in the shells ranged from 1.143 to 1.201 for 206Pb/207Pb and from 2.061 to 2.161 for 208Pb/206Pb. The isotopic signatures recorded in the sample shells correspond to similar ranges of Pb signatures reported for marine sediments from the same study area. In general, this work shows that LA-MC-ICP-MS is a suitable technique for determining spatially resolved lead isotopic signatures in bivalve shells and that it can be used to estimate the origin of Pb pollution in aquatic environments.

Tracing the Sources and Fate of NO3- in the Vadose Zone-Groundwater System of a Thousand-Year-Cultivated Region.

Excess nitrate (NO3-) loading in terrestrial and aquatic ecosystems can result in critical environmental and health issues. NO3--rich groundwater has been recorded in the Guanzhong Plain in the Yellow River Basin of China for over 1000 years. To assess the sources and fate of NO3- in the vadose zone and groundwater, numerous samples were collected via borehole drilling and field surveys, followed by analysis and stable NO3- isotope quantification. The results demonstrated that the NO3- concentration in 38% of the groundwater samples exceeded the limit set by the World Health Organization. The total NO3- stock in the 0-10 m soil profile of the orchards was 3.7 times higher than that of the croplands, suggesting that the cropland-to-orchard transition aggravated NO3- accumulation in the deep vadose zone. Based on a Bayesian mixing model applied to stable NO3- isotopes (δ15N and δ18O), NO3- accumulation in the vadose zone was predominantly from manure and sewage N (MN, 27-54%), soil N (SN, 0-64%), and chemical N fertilizer (FN, 4-46%). MN was, by far, the greatest contributor to groundwater NO3- (58-82%). The results also indicated that groundwater NO3- was mainly associated with the soil and hydrogeochemical characteristics, whereas no relationship with modern agricultural activities was observed, likely due to the time delay in the thick vadose zone. The estimated residence time of NO3- in the vadose zone varied from decades to centuries; however, NO3- might reach the aquifer in the near future in areas with recent FN loading, especially those under cropland-to-orchard transition or where the vadose zone is relatively thin. This study suggests that future agricultural land-use transitions from croplands to orchards should be promoted with caution in areas with shallow vadose zones and coarse soil texture.

Quantification of hydrogen isotopes by CF-LIBS in a W-based material (WZr) at atmospheric pressure: from ns towards ps

Tungsten-based materials are possible candidates as PFCs in future fusion devices. LIBS is one of the most suitable techniques for monitoring erosion and deposition processes including fuel retention, due to its versatility and ability to perform in situ measurements. By deploying ps-LIBS, instead of ns, the laser ablation occurs with fewer melting effects. This work compares ns- and ps- (CF)-LIBS characterization of WZr(D) samples, at the linear plasma generator at Magnum-PSI at the DIFFER. The laser energy has been optimized for both laser regimes, lowering the laser energy for the ns regime (from 19.9 mJ pulse−1 to 7.4 mJ pulse−1) to approximate to ps regime (0.3 mJ pulse−1). All the experimental measurements have been performed at Patm. The pure WZr samples have been analyzed in ambient air, while the WZrD sample measurements have been performed under Ar gas flow. The retained deuterium content varies from 4 at% to 0.3 at%.

The NUNAtak Ice Thinning (NUNAIT) Calculator for Cosmonuclide Elevation Profiles

Cosmogenic nuclides are widely used to constrain the landscape history of glaciated areas. At nunataks in continental polar regions with extremely arid conditions, cosmogenic nuclides are often the only method available to date the ice thinning history of the glacier. However, the amount of cosmogenic isotopes accumulated at the surface of nunataks depends not only on the length of time that rock has been exposed since the last deglaciation but also on the full history of the surface, including muon production under ice, exposure during previous interglacials, subaerial weathering rate, glacial erosion rate, and uplift rate of the nunatak. The NUNAtak Ice Thinning model (NUNAIT) simulates the cosmonuclide accumulation on vertical profiles, fitting the aforementioned parameters to a set of multi-isotope apparent ages from samples taken at different elevations over the ice-sheet surface. The NUNAIT calculator is an easy-to-use tool that constrains parameters that describe the geological history of a nunatak from a set of surface exposure ages.

Fukushima Nuclear Power Plant accident: Various issues with iodine distribution and medication orders.

Immediately after the Great East Japan Earthquake on March 11, 2011, the public could not receive accurate information concerning about the reality of the accident at the Fukushima Nuclear Power Plant because of communication problems with mobile phone base stations caused by power outages and the inadequate use of communication satellites between local governments. These telecommunications troubles caused not only a delay between the Japanese central government to local governments, but also a failure in conveying the seriousness of the accident to residents. The central government issued evacuation orders, but in some areas, a delay was seen in the time residents took to notice the orders. Some residents were forced to change their evacuation site several times and move to areas with higher radiation exposure. Although iodine preparations needed to be distributed to saturate the thyroid gland and reduce the uptake of iodine-131, a radioactive isotope, many municipalities were unable to secure them. Preparations were distributed on March 15, 2011 when the detectable amount of radioactive isotopes peaked, but only the Naraha and Miharu towns received them. At the time of the Fukushima Nuclear Power Plant accident, communication lines had already been interrupted by the major earthquake that struck on March 11, and information systems between local governments were not communicating well. With such a social infrastructure, residential evacuation orders were inadequate, and the delivery of medication was extremely difficult. The experience of the Fukushima Nuclear Power Plant accident suggests that the government should have distributed iodine preparations to residents living within a 30-km radius of the plant in advance, so that they could learn about the background and side effects of the drug beforehand. This distribution strategy is similar to that of targeted antivirus prophylaxis (TAP), which is an extralegal policy carried out in situations where face-to-face medical treatment is impossible because of an outbreak during a pandemic.

Quantification of curium isotopes in environmental samples: drawbacks, speciation and specific tracer

In this study, drawbacks of the use of 243Am as a tracer in order to quantify curium isotopes during a complex chemical procedure were highlighted. These drawbacks were investigated through a speciation computation simulation based on the compilation of over 50 stability constants. A new curium standard was then characterized and used to quantify a wide 244Cm activities range in environmental samples. Obtained results were in excellent agreement with spiked activities and more consistent than those obtained when using 243Am as tracer.

Accessory laboratory measurements to support quantification of hydrogen isotopes by in-situ LIBS from a robotic arm inside a fusion vessel

In order to try to improve spectral separation for hydrogen isotope detection in plasma facing components, a flow of noble gas at reduced pressure is proposed as alternative to atmospheric pressure experiments in air during maintenance of fusion vessels. To this aim the already realized compact LIBS probe has been equipped with a sealable tip where a noble gas could flow. The tip was in contact with the selected point of the target and its proper positioning was guaranteed by an adjustable metallic cone. Laboratory measurements were carried out by flowing either He or Ar on ITER-like tiles. A positive effect of Ar flow on Hα signal intensity was observed, while a significant narrowing of the Hα band was obtained upon He addition.Additional measurements on deuterium doped samples simulating the tile's composition in ITER divertor region were performed by applying a local vacuum in the point of analysis or utilizing the set-up in double pulse (DP) mode. These experiments were aimed at optimizing the acquisition parameters of the LIBS setup (e.g, single or double pulse excitation, gate delay, gate width, interpulse delay) when operated in different conditions (vacuum, atmospheric pressure, under gas flow) in order to resolve the two nearby emission bands Hα and Dα, still preserving a satisfactory Signal-to-Noise-Ratio (SNR). Finally, considerations on applicability of Calibration Free (CF) method for the quantification of hydrogen isotopes are presented.

Remote isotope detection and quantification using femtosecond filament-laser ablation molecular isotopic spectrometry

We demonstrate the detection and quantification of isotopes from solid samples remotely at a distance of 36 m. This was accomplished through the combination of femtosecond filaments and laser ablation molecular isotopic spectrometry (F2-LAMIS). Isotopically enriched graphite samples with varying 13C concentration were used and the F2-LAMIS emission was measured remotely using a fieldable spectrometer system. A standardless quantification approach was used to determine the corresponding isotopic ratios. The use of F2-LAMIS for the detection and quantification of isotopes at atmospheric pressure without the use of calibration standards opens the possibility to implement this technology for remote sensing of isotopes in field applications.

Determination of uranium and thorium isotopes in kaolinitic samples by ICP-MS/MS

The use of natural uranium and thorium long-lived isotopes was applied to study the evolution of kaolinitic materials. To do that, a radiochemical method for separation of Th and U in phyllosilicate samples was developed with the main aim of their analysis by ICP-MS/MS. Given the lack of certified phyllosilicate reference materials with certified isotope abundances, the method was tested using a stepwise approach. First, a preliminary setup was done using a sediment reference sample. Then, the extrapolation of this method to the samples of interest has been tested using a phyllosilicate sample certified for U and Th concentrations. The results showed that an extension of the plateau time of digestion in the used microwave system was peremptory as to get full digestion of the sample. The use of the isotope dilution technique allowed both the quantification of major isotopes (238U and 232Th) simultaneous to the determination of isotope ratios (234U/238U, 235U/238U for quality control and 230Th/232Th). The established method was applied to six kaolinitic samples from the Iberian Range (NE Spain), showing the potential of this isotope approach for the characterization of their time evolution.

(Invited) Discussion on Use of Controls and Quantitative Verification of Electrochemical Ammonia Production

The research community focused on the development of heterogeneous electrocatalysts for low temperature electrochemical nitrogen reduction to ammonia continues to see an increasing number of publication contributions on electrocatalyst synthesis and performance testing, with few studies conducting quantitative and thorough verification of ammonia production data. With the recent publication of recommended guidelines and procedures for controls and isotopic verification of ammonia synthesis, we need to continue to discuss as a research community what is necessary to support electrocatalyst design and synthesis efforts. Some open questions for continued discussion include: What level of experimental controls and isotopic quantification are necessary, and how should these experiments and results be reported? Are we missing ambient or contaminant influences in our ammonia measurements? What studies published thus far represent the highest quality of work, and should these studies be used to demonstrate electrocatalyst design pathways? How can we promote and proceed with repeating published work to verify electrocatalyst performance? What are the experimental challenges that researchers are facing in being able to repeatedly and accurately measure ammonia produced by heterogeneous electrocatalyst surfaces? In this talk, we will discuss these and other questions facing our NRR research community today.

Highly Sensitive Real-Time Isotopic Quantification of Water by ATR-FTIR.

A method has been developed to reliably quantify the isotopic composition of liquid water, requiring only immersion of a “ReactIR” probe in the sample under test. The accuracy and robustness of this method has been extensively tested using a deuterium/protium system, and substantial improvements in sensitivity were obtained using highly novel chemical signal amplification methods demonstrating a standard deviation of 247 ppb D (a δD of 1.6 ‰). This compares favorably with other more costly and time-consuming techniques and is over 20 times more sensitive than any previously published FTIR study. Computational simulations of a model system match the experimental data and show how these methods can be adapted to a tritium/protium system.