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In this comprehensive study, we evaluated the feasibility of using hydrogen instead of helium as a carrier gas in a GC-MS/MS system for pesticide residue analysis, spanning three matrices: pepper, tomato, and zucchini. Initial assessments focused on the ion source's chemical inertness, employing nitrobenzene as a benchmark to monitor the hydrogenation process. A method with a duration of less than 12 minutes was developed, achieving good chromatographic peak resolution attributable to the enhanced chromatographic performance of hydrogen as a carrier gas. The study emphasized the optimization of system parameters, testing various ion source temperatures, detector voltages, and injection volumes. Sensitivity assessments, based on the DG-SANTE criteria, indicated that the majority of compounds were identifiable at a concentration of 5 μg kg -1 (81% in tomato, 84% in pepper and 73% in zucchini). Detailed validation for reproducibility, matrix effects, and linearity across 150 pesticides unveiled generally favorable outcomes, with a notable majority of compounds displaying low matrix effects, satisfactory linearity ranges and good reproducibility with most compounds returning a relative standard deviation (RSD) below 10%. When applied to 15 real samples, the hydrogen-based system's performance was juxtaposed against a helium-based counterpart, revealing that results are very comparable between both systems. This comparative approach highlights hydrogen's potential as a reliable and efficient carrier gas in pesticide residue analysis for routine food control laboratories, overcoming difficulties resulting from the lack of helium supplies.

Purpose: In this study, we proposed a new sensitive quantitative method for detecting helium in human blood by gas chromatography-selected-ion monitoring (SIM)-mass spectrometry (GC-SIM-MS) using naturally existing neon-21 in air as internal standard (IS).Methods: GC-SIM-MS analysis was performed on a double TC-Molsieve 5A capillary column (total length 60 m) for the separation of permanent gases by a single-run experiment. By using hydrogen as the carrier gas, the analyte (helium) and IS (neon-21) were separated on the double column, and detected at m/z 4 and 21, respectively. The ratio of the peak area of helium-to-neon-21 was used for obtaining the calibration curve for helium determination.Results: The limits of detection and quantification of helium under the present GC-SIM-MS conditions were as low as 1.8 and 6.0 ppm, respectively. The proposed GC-SIM-MS method also showed high repeatability with relative standard deviation at 1.3-5.1%, indicating that the use of neon-21 as IS was valid for reliable helium assays. The successful quantification of helium in the headspace of vacuum blood collection tubes containing the whole blood from four humans who died of helium inhalation was achieved using the proposed neon-21-aided GC-SIM-MS method; the values obtained for helium were 24-497 ppm.Conclusions: The proposed GC-SIM-MS method in combination with the naturally existing neon-21 as IS is most recommendable for quantitative assays of helium in biological samples because of its simplicity and extremely high sensitivity. [ABSTRACT FROM AUTHOR]

The combination of helium charge transfer dissociation mass spectrometry (He-CTD-MS) with ultrahigh performance liquid chromatography (UHPLC) is presented for the analysis of a complex mixture of acidic and neutral human milk oligosaccharides (HMOs). The research focuses on the identification of the monosaccharide sequence, the branching patterns, the sialylation/fucosylation arrangements, and the differentiation of isomeric oligosaccharides in the mixture. Initial studies first optimized the conditions for the UHPLC separation and the He-CTD-MS conditions. Results demonstrate that He-CTD is compatible with UHPLC timescales and provides unambiguous glycosidic and cross-ring cleavages from both the reducing and the nonreducing ends, which is not typically possible using collision-induced dissociation. He-CTD produces informative fragments, including 0,3An and 0,4An ions, which have been observed with electron transfer dissociation, electron detachment dissociation, and ultraviolet photodissociation (UVPD) and are crucial for differentiating the α-2,3- versus α-2,6-linked sialic acid (Neu5Ac) residues present among sialyllacto-N-tetraose HMOs. In addition to the linkage positions, He-CTD is able to differentiate structural isomers for both sialyllacto-N-tetraoses and lacto-N-fucopentaoses structures by providing unique, unambiguous cross-ring cleavages of types 0,2An, 0,2Xn, and 1,5An while preserving most of the labile Neu5Ac and fucose groups., (© The Author(s) 2022. Published by Oxford University Press. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.)

All products labeled as sterile are required to be free of microbial contamination throughout their shelf life (obligatory critical quality attribute). Container closure integrity (CCI) needs to be addressed with a holistic life cycle strategy comprising adequate primary packaging components selection and the assessment of critical unit operations and critical process parameters (CPPs) according to quality by design (QbD) principles. The helium leak method is currently the most sensitive CCI test method and preferably used for the initial container closure system (CCS) qualification and characterization studies. Currently, two different measuring principles are used in the pharmaceutical industry, and no data is available in the public domain for typical method performance parameters such as accuracy, precision, intermediate-precision, and limit of quantification of the method. Furthermore, the performance of different types and sizes of artificial leaks as well as certified helium leak standards have not yet been characterized across different test laboratories. In this multicompany study, we shared 17 artificially prepared leak samples using the most common types of artificial leaks in relevant nominal size ranges that are commercially available or can be easily prepared in a laboratory. Each participating company generated results according to their in-house methods, applying their established test parameters as the aim of the study was not to create a standard for helium leak measurements, but to compare real-world performance between different laboratories. Consequently, this study is not an interlaboratory study using the same test method across laboratories., (© PDA, Inc. 2022.)

Establishing when, and from where, carbon, nitrogen and water were delivered to Earth is a fundamental objective in understanding the origin of habitable planets such as Earth. Yet, volatile delivery to Earth remains controversial 1-5 . Krypton isotopes provide insights on volatile delivery owing to their substantial isotopic variations among sources 6-10 , although pervasive atmospheric contamination has hampered analytical efforts. Here we present the full suite of krypton isotopes from the deep mantle of the Galápagos and Iceland plumes, which have the most primitive helium, neon and tungsten isotopic compositions 11-16 . Except for 86 Kr, the krypton isotopic compositions are similar to a mixture of chondritic and atmospheric krypton. These results suggest early accretion of carbonaceous material by proto-Earth and rule out any combination of hydrodynamic loss with outgassing of the deep or shallow mantle to explain atmospheric noble gases. Unexpectedly, the deep-mantle sources have a deficit in the neutron-rich 86 Kr relative to the average composition of carbonaceous meteorites, which suggests a nucleosynthetic anomaly. Although the relative depletion of neutron-rich isotopes on Earth compared with carbonaceous meteorites has been documented for a range of refractory elements 1,17,18 , our observations suggest such a depletion for a volatile element. This finding indicates that accretion of volatile and refractory elements occurred simultaneously, with krypton recording concomitant accretion of non-solar volatiles from more than one type of material, possibly including outer Solar System planetesimals., (© 2021. The Author(s), under exclusive licence to Springer Nature Limited.)

Two statistically based testing procedures, a zero-failure test and a one-failure test, are proposed for demonstrating that a vial capping process has an acceptably low rate of failed seals, i.e., nonintegral container closures, or leaky vials. These tests are developed for use with the standard helium-leak test method that measures the amount of escaped helium from a capped vial. The amount of escaped helium is a continuous measurement, and a vial is said to be leaky if the measurement exceeds a threshold and not leaky if it does not. Not leaky measurements are often less than the lower limit of validation, i.e., left-censored. By using the continuous measurements that describe the extent of leaking instead of the binary measurements, leaky or not leaky, the proposed tests are able to reach similar conclusions as tests using binary measurements but with much smaller sample sizes. The proposed tests can handle any number of measurements less than the lower limit of validation., (© PDA, Inc. 2021.)

Urban groundwater management requires a thorough and robust scientific understanding of flow and transport processes. 3 H/ 3 He apparent ages have been shown to efficiently help provide important groundwater-related information. However, this type of analysis is expensive as well as labor- and time-intensive, and hence limits the number of potential sampling locations. To overcome this limitation, we established an inter-relationship between 3 H/ 3 He apparent groundwater ages and 4 He concentrations analyzed in the field with a newly developed portable gas equilibrium membrane inlet mass spectrometer (GE-MIMS) system, and demonstrated that the results of the simpler GE-MIMS system are an accurate and reliable alternative to sophisticated laboratory based analyses. The combined use of 3 H/ 3 He lab-based ages and predicted ages from the 3 H/ 3 He- 4 He age relationship opens new opportunities for site characterization, and reveals insights into the conceptual understanding of groundwater systems. For our study site, we combined groundwater ages with hydrochemical data, water isotopes ( 18 O and 2 H), and perchloroethylene (PCE) concentrations (1) to identify spatial inter-aquifer mixing between artificially infiltrated groundwater and water originating from regional flow paths and (2) to explain the spatial differences in PCE contamination within the observed groundwater system. Overall, low PCE concentrations and young ages occur when the fraction of artificially infiltrated water is high. The results obtained from the age distribution analysis are strongly supported by the information gained from the isotopic and hydrochemical data. Moreover, for some wells, fault-induced aquifer connectivity is identified as a preferential flow path for the transport of older groundwater, leading to elevated PCE concentrations., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

The Guaraní Aquifer System (SAG) is the largest transboundary aquifer in Latin America, extending beneath parts of Brazil, Paraguay, Argentina, and Uruguay. This paper presents the results of recent hydrogeological studies in the southern portion of the SAG. Locally, the abundance of surface water bodies precluded the use of conventional hydrological tools to characterize groundwater flows. Geological, hydrochemical and environmental isotope investigations were integrated to postulate a revised hydrogeological conceptual model. The revised geological model has provided a better definition of the geometry of the aquifer units and outlined the relevance of regional faults in controlling flow patterns. The new potentiometric map is consistent with groundwater flow from the SAG outcrops to the centre of the Corrientes Province, where upwards flows were identified. Hydrochemical and isotope data confirmed the widespread occurrence of mixing. Noble gas isotopes dissolved in groundwater ( 4 He and 81 Kr/Kr) provided residence times ranging from recent recharge up to 770 ± 130 ka. Groundwater age modelling confirmed the role of the geological structures in controlling groundwater flow. The southern sector of the SAG is a multilayer aquifer system with vertical flows and deep regional discharge near the Esteros del Iberá wetland area and along the Paraná and Uruguay rivers.

Neutron detection using nuclear emulsions can offer an alternative in personal dosimetry. The production of emulsions and their quality have to be well controlled with respect to their application in dosimetry. Nuclear emulsions consist mainly of gelatin and silver halide. Gelatin contains a significant amount of hydrogen, which can be used for fast neutron detection. The addition of B-10 in the emulsion is convenient for thermal neutron detection. In this paper, standard nuclear emulsions BR-2 and nuclear emulsions BR-2 enriched with boron produced at the Slavich Company, Russia, were applied for evaluation of fast and thermal neutron fluences. The results were obtained by calculation from the presumed emulsion composition without prior calibration. Evidence that nuclear emulsions used in the experiment are suitable for neutron dosimetry is provided., (© The Author(s) 2019. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.)

An increasing number of suicidal asphyxiation with a plastic bag with inert gases, and in particular helium (He), have been reported from numerous countries over the last decade. These cases are differently managed and lead to different and variable interpretations. Based on the 12 last cases analysed in the laboratory and on the review of the most recent literature about this topic, updated autopsy guidelines for sampling have been proposed regarding to the samples choice and analytical challenges required by the gaseous state of this substance. Biological samples from airways (lungs lobe) followed by brain and cardiac blood are the best matrices to take during the autopsy to diagnose He exposure. Gaseous samples from trachea, pulmonary bronchi, gastric and cardiac areas are also recommended as alternative samples. The anatomical site of sampling must be carefully detailed, and to this end, forensic imaging constitutes a beneficial tool. Even if He detection is sufficient to conclude to He exposure, He concentrations in samples may be related to He exposure conditions (duration, breathing rate, etc.). A quantification in biological samples could be helpful to document more precisely the case. He concentrations in gaseous samples are reported up to 6.0 μmol/mL (tracheal gas), 2.4 μmol/mL (pulmonary gas), 0.64 μmol/mL (cardiac gas) and 12 μmol/mL (gastric gas). He concentrations in solid/liquid samples are reported up to 28 μmol/g (lungs) and 0.03 μmol/g (cardiac blood). The other matrices usually sampled during autopsy such as urine, peripheral blood, liver, fat matter and kidney appear as not relevant.

We describe the results obtained on a set of organic samples that have been part of the experiment "Photochemistry on the Space Station (PSS)" on the EXPOSE-R2 mission conducted on the EXPOSE-R facility situated outside the International Space Station (ISS). The organic samples were prepared in the Catania laboratory by 200 keV He + irradiation of N 2 :CH 4 :CO icy mixtures deposited at 17 K, on vacuum UV (VUV) transparent MgF 2 windows. This organic material contains different chemical groups, including triple CN bonds, that are thought to be of interest for astrobiology. It is widely accepted that materials similar to that produced in the laboratory by ion irradiation of frozen ices could be present in some astrophysical environments such as comets. Once expelled from comets, these materials are exposed to solar radiation during their interplanetary journey. In the young Solar System, some of these processed materials could have reached early Earth and contributed to its chemical and prebiotic evolution. The samples were exposed for 16 months to the unshielded solar UV photons. It was found that, if an interplanetary dust particle (IDP) containing organic material (50% vol) is large enough (>20-30 μm), relevant chemical groups, such as those containing the CN triple bond, can survive for many years (>10 4 years) in the interplanetary medium.

We have developed the first laboratory for (U-Th-Sm)/He thermochronology measurements in South America. Helium is measured using a high-sensitivity magnetic sector mass spectrometer (GVI-Helix-SFT) and a double focusing single collector inductively coupled plasma mass spectrometer (Thermo Scientific ELEMENT2) is used for U, Th and Sm determinations. Repeated analyses of fragments of Durango fluorapatite crystals yields an average age of 31.6 ± 1.6 Ma (2σ) (n=62). This overlaps the long-term average of Durango fluorapatite measured in laboratories worldwide. The analysis of multiple single apatite crystals of a Precambrian basement sample from Serra do Mar, southeastern Brazil, yields an average He age (60.5 ± 8.7 Ma; n=8) that overlaps that measured in the SUERC laboratory (59.6 ± 3 Ma; n=3). This confirms that the UNESP laboratory is capable of routinely measuring the (U-Th-Sm)/He ages of single apatite crystals.

Liquid helium (LHe) is used as a cryogen in a variety of applications involving superconductivity and is routinely monitored for conducting low-temperature experiments. Thermoacoustic oscillations, which are inevitably present inside closed LHe containers, are utilized for level detection by sensing the vibrations at the warm end of a thin capillary tube inserted into the Dewar. The position of the capillary tube at which a sudden change occurs in these oscillations is manually sensed to identify the liquid level. The present work proposes a novel hardware design to identify the thermoacoustic oscillations in a reliable way using an accelerometer driven by an Arduino microcontroller. Further, an automated approach has been devised to quantify the rate of change of these helium oscillations to measure the LHe level. The proposed method has been tested during several trials on a 120 L and 100 L capacity Dewar using the proposed hardware, and the mean error in measuring the LHe level was calculated to be less than 1 cm in comparison with the gold standard niobium-titanium level sensor. The results encourage the use of the proposed method to evolve as a cost-effective alternative to the widely used superconducting level sensors in measuring LHe level.

Prefilled syringes (PFSs) are increasingly preferred over vials as container closure systems (CCSs) for injectable drug products when facilitated or self-administration is required. However, PFSs are more complex compared to CCSs consisting of vial, rubber stopper, and crimp cap. Container closure integrity (CCI) assurance and verification has been a specific challenge for PFSs as they feature several sealing areas. A comprehensive understanding of the CCS is necessary for an appropriate CCI assessment as well as for packaging development and qualification. A comprehensive CCI assessment of 6 different PFSs from 3 different manufacturers (including 1 polymeric PFS) was conducted using helium leak testing. PFS components were manipulated to systematically assess the contribution of the different sealing areas to CCI, namely rigid needle shield (RNS)/needle, RNS/tip cone, and the individual ribs of a syringe plunger. The polymeric PFS required an equilibrium measurement for accurate container closure integrity testing. The different sealing areas and a single plunger rib were shown to provide adequate CCI. Acceptable tip cap movement until the point of CCI failure was estimated. The assessment of acceptable tip cap movement demonstrated the importance of considering the RNS/tip cone seal design to ensure CCI of the PFS upon post assembly possesses and shipment., (Copyright © 2018 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.)

Helium is nontoxic at standard conditions, plays no biological role, and is found in trace amounts in human blood. Helium can be dangerous if inhaled to excess, since it is a simple tissue hypoxia and so displaces the oxygen needed for normal respiration. This report presents a fatal case of a middle-aged male victim who died from self-administered helium exposure. For the first time, the quantification of the helium levels in gastric and lung air and in blood samples was achieved using gas chromatography-mass spectrometry after airtight sampling. The results of the toxicological investigation showed that death was caused directly by helium exposure. However, based on the pathomorphological changes detected during the forensic autopsy, we suppose that the fatal outcome was the result of the lack of oxygen after inhalation.

Excimer lasers, widely used in the semiconductor industry, are crucial for analyzing the purity of premix laser gases for the purpose of controlling stable laser output power. In this study, we designed a system for analyzing impurities in pure neon (Ne) base gas by customized GC. Impurities in pure neon (H2 and He), which cannot be analyzed at the sub-μmol/mol level using commercial GC detectors, were analyzed by a customized pulsed-discharge Ne ionization detector (PDNeD) and a pressurized injection thermal conductivity detector using Ne as the carrier gas (Pres. Inj. Ne-TCD). From the results, trace species in Ne were identified with the following detection limits: H2, 0.378μmol/mol; O2, 0.119μmol/mol; CH4, 0.880μmol/mol; CO, 0.263μmol/mol; CO2, 0.162μmol/mol (PDNeD); and He, 0.190μmol/mol (Pres. Inj. Ne-TCD). This PDNeD and pressurized injection Ne-TCD technique thus developed permit the quantification of trace impurities present in high-purity Ne., (Copyright © 2016. Published by Elsevier B.V.)

Purpose To assess the feasibility and optimize the accuracy of the multibreath wash-in hyperpolarized helium 3 ((3)He) approach to ventilation measurement by using magnetic resonance (MR) imaging as well as to examine the physiologic differences that this approach reveals among nonsmokers, asymptomatic smokers, and patients with chronic obstructive pulmonary disease (COPD). Materials and Methods All experiments were approved by the local institutional review board and compliant with HIPAA. Informed consent was obtained from all subjects. To measure fractional ventilation, the authors administered a series of identical normoxic hyperpolarized gas breaths to the subject; after each inspiration, an image was acquired during a short breath hold. Signal intensity buildup was fit to a recursive model that regionally solves for fractional ventilation. This measurement was successfully performed in nine subjects: three healthy nonsmokers (one man, two women; mean age, 45 years ± 4), three asymptomatic smokers (three men; mean age, 51 years ± 5), and three patients with COPD (three men; mean age, 59 years ± 5). Repeated measures analysis of variance was performed, followed by post hoc tests with Bonferroni correction, to assess the differences among the three cohorts. Results Whole-lung fractional ventilation as measured with hyperpolarized (3)He in all subjects (mean, 0.24 ± 0.06) showed a strong correlation with global fractional ventilation as measured with a gas delivery device (R(2) = 0.96, P < .001). Significant differences between the means of whole-lung fractional ventilation (F2,10 = 7.144, P = .012) and fractional ventilation heterogeneity (F2,10 = 7.639, P = .010) were detected among cohorts. In patients with COPD, the protocol revealed regions wherein fractional ventilation varied substantially over multiple breaths. Conclusion Multibreath wash-in hyperpolarized (3)He MR imaging of fractional ventilation is feasible in human subjects and demonstrates very good global (whole-lung) precision. Fractional ventilation measurement with this physiologically realistic approach reveals significant differences between patients with COPD and healthy subjects. To minimize error, several sources of potential bias must be corrected when calculating fractional ventilation. (©) RSNA, 2016 Online supplemental material is available for this article.

Introduction: Toxicological findings in deaths by asphyxiation due to a pure inert gas like helium are rare. We present three suicide cases of asphyxial death attributed to anoxia caused by inhalation of helium in a plastic bag positioned over the head., Methods: In one case, lung tissue, brain tissue and heart blood were obtained during standard autopsy procedures. In two cases, samples were obtained differently: heart blood, femoral blood, brain tissue, lung tissue and/or air from the lungs were directly sealed into headspace vials during autopsy. Air from the lungs was collected using a syringe and transferred into an aluminum gas sampling bag which was heat sealed as soon as possible. Semi-quantitative gas analyses were performed using headspace gas chromatography-thermal conductivity detection (HS-GC/TCD) with a molsieve column capable of separating permanent gasses. Nitrogen was used as carrier gas., Results: In the first case no helium was detected in lung tissue, brain tissue and heart blood. In the second case the presence of helium was detected in lung tissue (approximately 5% helium in gaseous phase) but not in femoral blood. In the third case the presence of helium was detected in air from the lungs (0.05%), lung tissue (0.4%), brain tissue (0.1%) and heart blood (0.04%)., Conclusions: Helium is easily lost if sampling is not performed properly. The presented cases suggest that quick sample collection of various matrices during autopsy is suitable to detect gasses like helium in postmortem cases. Use of HS-GC/TCD enables to detect an inert gas like helium., (Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.)

The present research is focused on the use and evaluation of a novel helium ionization detector, defined as barrier discharge ionization detector (BID), within the context of (low-)flow modulation comprehensive two-dimensional gas chromatography (FM GC×GC). The performance of the BID device was compared to that of a flame ionization detector (FID), under similar FM GC×GC conditions. Following development and optimization of the FM GC×GC method, the BID was subjected to fine tuning in relation to acquisition frequency and discharge flow. Moreover, the BID performance was measured and compared to that of the FID, in terms of extra-column band broadening, sensitivity and dynamic range. The comparative study was carried out by using standard compounds belonging to different chemical classes, along with a sample of diesel fuel. Advantages and disadvantages of the BID system, also within the context of FM GC×GC, are critically discussed. In general, the BID system was characterized by a more limited dynamic range and increased sensitivity, compared to the FID. Additionally, BID and FID contribution to band broadening was found to be similar under the operational conditions applied. Particular attention was devoted to the behaviour of the FM GC×GC-BID system toward saturated and aromatic hydrocarbons, for a possible future use in the field of mineral-oil food contamination research., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Apparent ages obtained from the measured concentrations of environmental tracers have the potential to inform recharge rates, flow rates, and assist in the calibration of groundwater models. A number of studies have investigated sources of error in the relationships between the apparent ages, and the age assumed by models to relate this quantity to an aquifer property (e.g., recharge). These studies have also provided a number of techniques for correcting the known biases of apparent ages. In this paper, we review some of the concepts of age bias. We then demonstrate this bias through the use on four numerical examples, and assess the accuracy of correction methods in overcoming this bias. We examine this for CFCs, SF6, 3H/3He, 39Ar, and 14C. We demonstrate that in our four simple steady-state aquifer examples, bias occurs for a wide range of environmental tracers and flow configurations. When applying correction methods, we found that the values obtained are limited by the model assumptions. Models accounting for exchange with aquitards represent whole mobile zones and not discrete well screens. Mean transit times (comparable to mean ages) obtained from lumped parameter models deviate from actual values as the assumed distribution varies from the actual distribution. Methods that use multiple tracer ages are limited to ranges where both tracers report apparent ages. Our findings suggest that the incorporation of environmental tracer data into the understanding of groundwater systems requires approaches such as the direct use of concentrations, or the simulation of full age distributions., (© 2014, National Ground Water Association.)

In this study, we use PFLOTRAN, a highly scalable, parallel, flow, and reactive transport code to simulate the concentrations of 3H, 3He, CFC-11, CFC-12, CFC-113, SF6, 39Ar, and the mean groundwater age in heterogeneous fields on grids with an excess of 10 million nodes. We utilize this computational platform to simulate the concentration of multiple tracers in high-resolution, heterogeneous 2D and 3D domains, and calculate tracer-derived ages. Tracer-derived ages show systematic biases toward younger ages when the groundwater age distribution contains water older than the maximum tracer age. The deviation of the tracer-derived age distribution from the true groundwater age distribution increases with increasing heterogeneity of the system. However, the effect of heterogeneity is diminished as the mean travel time gets closer to the tracer age limit. Age distributions in 3D domains differ significantly from 2D domains. 3D simulations show decreased mean age, and less variance in age distribution for identical heterogeneity statistics. High-performance computing allows for investigation of tracer and groundwater age systematics in high-resolution domains, providing a platform for understanding and utilizing environmental tracer and groundwater age information in heterogeneous 3D systems., (© 2013, National Ground Water Association.)

The goal of the study is to assess the feasibility of characterizing the caprock integrity by utilizing sampled helium (He) concentration in fluids and temperature measurement prior to CO2 injection. A series of simulations representing pre-CO2 injection phase was conducted to reveal the spatial distribution of groundwater, temperature, and He concentration under various geologic conditions of topographically driven basin. Then, their profiles in preinjection conditions were compared with dynamic signatures of both injection-induced pressure and leaked brine concentration at post-CO2 injection conditions. In the topographic basin, He and heat transports generally show analogous transport except the low-permeability basin where the conductive heat and diffusive solute transports are the primary transport mechanisms. The transition occurred at permeabilities between 10(-15) and 10(-14) m2. Inclusion of low-k layer (low-k layer: 10(-16) m2 and surrounding basin: 10(-13) m2) segregates shallow and deep groundwater system and creates a 3-km single large free convection of groundwater driven by unevenly distributed thermal profile of basin. Finally, He and temperature profiles with high-k pathways at pre-CO2 injection scenarios and NaCl mass fractions at post-CO2 injection showed systematic trends and relationships, suggesting that proper understanding of these trends will aid to identify the seal integrity., (© 2014, National Ground Water Association.)

Applications of the Helium (He) method known so far consisted mainly of 4He measurements using a special mass spectrometer. 4He measurements for groundwater dating purposes can be replaced by total He (3He+4He) concentration measurements because the content of 3He can be ignored. The concentrations of 3He are very low and 3He/4 He ratios do not exceed 1.0·10(-5) in most cases. In this study, the total He concentrations in groundwater were determined using the gas chromatographic (GC) method as an alternative to methods based on spectrometry measurement. He concentrations in groundwater were used for the determination of residence time and groundwater circulation. Additionally, the radiocarbon method was used to determine the value of the external He flux (JHe) in the study area. Obtained low He concentrations and their small variation within the ca. 65 km long section along which groundwater flows indicate that it is likely there is relatively short residence time and a strong hydraulic connection between the aquifers. The estimated residence time (ca. 3000 years) is heavily dependent on the great uncertainty of the He concentration resulting from the low concentrations of He, the external 4He flux value adopted for calculation purposes and the 14C ages used to estimate the external 4He flux., (© 2015, National Ground Water Association.)

Purpose: In MR-velocity phase-contrast measurements, increasing the encoding bipolar gradient, i.e., decreasing the field of speed, usually improves measurement precision. However, in gases, fast diffusion during the bipolar gradient pulses may dramatically decrease the signal-to-noise ratio, thus degrading measurement precision. These two effects are contradictory. This work aims at determining the optimal sequence parameters to improve the velocity measurement precision., Theory and Methods: This work presents the theoretical optimization of bipolar gradient parameters (duration and amplitude) to improve velocity measurement precision. An analytical approximation is given as well as a numerical optimization. It is shown that the solution depends on the diffusion coefficient and T2 *. Experimental validation using hyperpolarized (3) He diluted in various buffer gases ((4) He, N2 , and SF6 ) is presented at 1.5 Tesla (T) in a straight pipe., Results: Excellent agreement was found with the theoretical results for prediction of optimal field of speed and good agreement was found for the precision in measured velocity, but for SF6 buffered gas., Conclusion: The theoretical predictions were validated, providing a way to optimize velocity mapping in gases., (Copyright © 2013 Wiley Periodicals, Inc.)

The Younger Dryas stadial, a cold event spanning 12,800 to 11,500 years ago, during the last deglaciation, is thought to coincide with the last major glacial re-advance in the tropical Andes. This interpretation relies mainly on cosmic-ray exposure dating of glacial deposits. Recent studies, however, have established new production rates for cosmogenic (10)Be and (3)He, which make it necessary to update all chronologies in this region and revise our understanding of cryospheric responses to climate variability. Here we present a new (10)Be moraine chronology in Colombia showing that glaciers in the northern tropical Andes expanded to a larger extent during the Antarctic cold reversal (14,500 to 12,900 years ago) than during the Younger Dryas. On the basis of a homogenized chronology of all (10)Be and (3)He moraine ages across the tropical Andes, we show that this behaviour was common to the northern and southern tropical Andes. Transient simulations with a coupled global climate model suggest that the common glacier behaviour was the result of Atlantic meridional overturning circulation variability superimposed on a deglacial increase in the atmospheric carbon dioxide concentration. During the Antarctic cold reversal, glaciers advanced primarily in response to cold sea surface temperatures over much of the Southern Hemisphere. During the Younger Dryas, however, northern tropical Andes glaciers retreated owing to abrupt regional warming in response to reduced precipitation and land-surface feedbacks triggered by a weakened Atlantic meridional overturning circulation. Conversely, glacier retreat during the Younger Dryas in the southern tropical Andes occurred as a result of progressive warming, probably influenced by an increase in atmospheric carbon dioxide. Considered with evidence from mid-latitude Andean glaciers, our results argue for a common glacier response to cold conditions in the Antarctic cold reversal exceeding that of the Younger Dryas.

This article reports the development of programmable system-on-chip (PSoC)-based embedded readout designs for liquid helium level sensors using resistive liquid vapor discriminators. The system has been built for the measurement of liquid helium level in a concave-bottomed, helmet-shaped, fiber-reinforced plastic cryostat for magnetoencephalography. This design incorporates three carbon resistors as cost-effective sensors, which are mounted at desired heights inside the cryostat and were used to infer the liquid helium level by measuring their temperature-dependent resistance. Localized electrical heating of the carbon resistors was used to discriminate whether the resistor is immersed in liquid helium or its vapor by exploiting the difference in the heat transfer rates in the two environments. This report describes a single PSoC chip for the design and development of a constant current source to drive the three carbon resistors, a multiplexer to route the sensor outputs to the analog-to-digital converter (ADC), a buffer to avoid loading of the sensors, an ADC for digitizing the data, and a display using liquid crystal display cum light-emitting diode modules. The level sensor readout designed with a single PSoC chip enables cost-effective and reliable measurement system design., (© 2014 Society for Laboratory Automation and Screening.)

Ion mobility instruments that utilize nitrogen as buffer gas are often preceded by an ion trap and accumulation region that also uses nitrogen, and for different inert gases, no significant effects upon performance are expected for ion mobility spectrometry (IMS) of larger ions. However, we have observed significantly improved performance for an ion funnel trap upon adding helium; the signal intensities for higher m/z species were improved by more than an order of magnitude compared to using pure nitrogen. The effect of helium upon IMS resolving power was also studied by introducing a He/N2 gas mixture into the drift cell, and in some cases, a slight improvement was observed compared to pure N2. The improvement in signal can be largely attributed to faster and more efficient ion ejection into the drift tube from the ion funnel trap.

Multiple-breath washout hyperpolarized (3)He MRI was used to calculate regional parametric images of fractional ventilation (r) as the ratio of fresh gas entering a volume unit to the total end inspiratory volume of the unit. Using a single dose of inhaled hyperpolarized gas and a total acquisition time of under 1 min, gas washout was measured by dynamic acquisitions during successive breaths with a fixed delay. A two-dimensional (2D) imaging protocol was investigated in four healthy subjects in the supine position, and in a second protocol the capability of extending the washout imaging to a three-dimensional (3D) acquisition covering the whole lungs was tested. During both protocols, subjects were breathing comfortably, only restricted by synchronization of breathing to the sequence timings. The 3D protocol was also successfully tested on one patient with cystic fibrosis. Mean r values from each volunteer were compared with global gas volume turnover, as calculated from flow measurement at the mouth divided by total lung volume (from MRI images), and a significant correlation (r = 0.74, P < 0.05) was found. The effects of gravity on R were investigated, and an average decrease in r of 5.5%/cm (Δr = 0.016 ± 0.006 cm(-1)) from posterior to anterior was found in the right lung. Intersubject reproducibility of r imaging with the 2D and 3D protocol was tested, and a significant correlation between repeated experiments was found in a pixel-by-pixel comparison. The proposed methods can be used to measure r on a regional basis.

Littlefield Springs discharge about 1.6 m³ /s along a 10-km reach of the Virgin River in northwestern Arizona. Understanding their source is important for salinity control in the Colorado River Basin. Environmental tracers suggest that Littlefield Springs are a mixture of older groundwater from the regional Great Basin carbonate aquifer and modern (post-1950s) seepage from the Virgin River. While corrected ¹⁴C apparent ages range from 1 to 9 ka, large amounts of nucleogenic ⁴He and low ³He/⁴He ratios suggest that the carbonate aquifer component is likely even older Pleistocene recharge. Modeled infiltration of precipitation, hydrogeologic cross sections, and hydraulic gradients all indicate recharge to the carbonate aquifer likely occurs in the Clover and Bull Valley Mountains along the northern part of the watershed, rather than in the nearby Virgin Mountains. This high-altitude recharge is supported by relatively cool noble-gas recharge temperatures and isotopically depleted δ²H and δ¹⁸O. Excess (crustal) SF₆ and ⁴He precluded dating of the modern component of water from Littlefield Springs using SF₆ and ³H/³He methods. Assuming a lumped-parameter model with a binary mixture of two piston-flow components, Cl⁻ /Br⁻, Cl⁻ /F⁻, δ²H, and CFCs indicate the mixture is about 60% Virgin River water and 40% groundwater from the carbonate aquifer, with an approximately 30-year groundwater travel time for Virgin River seepage to re-emerge at Littlefield Springs. This suggests that removal of high-salinity sources upstream of the Virgin River Gorge would reduce the salinity of water discharging from Littlefield Springs into the Virgin River within a few decades., (Published 2013. This article is a U.S. Government work and is in the public domain in the USA.)

Fluids trapped as inclusions within minerals can be billions of years old and preserve a record of the fluid chemistry and environment at the time of mineralization. Aqueous fluids that have had a similar residence time at mineral interfaces and in fractures (fracture fluids) have not been previously identified. Expulsion of fracture fluids from basement systems with low connectivity occurs through deformation and fracturing of the brittle crust. The fractal nature of this process must, at some scale, preserve pockets of interconnected fluid from the earliest crustal history. In one such system, 2.8 kilometres below the surface in a South African gold mine, extant chemoautotrophic microbes have been identified in fluids isolated from the photosphere on timescales of tens of millions of years. Deep fracture fluids with similar chemistry have been found in a mine in the Timmins, Ontario, area of the Canadian Precambrian Shield. Here we show that excesses of (124)Xe, (126)Xe and (128)Xe in the Timmins mine fluids can be linked to xenon isotope changes in the ancient atmosphere and used to calculate a minimum mean residence time for this fluid of about 1.5 billion years. Further evidence of an ancient fluid system is found in (129)Xe excesses that, owing to the absence of any identifiable mantle input, are probably sourced in sediments and extracted by fluid migration processes operating during or shortly after mineralization at around 2.64 billion years ago. We also provide closed-system radiogenic noble-gas ((4)He, (21)Ne, (40)Ar, (136)Xe) residence times. Together, the different noble gases show that ancient pockets of water can survive the crustal fracturing process and remain in the crust for billions of years.

To enable a wider use of dissolved noble gas concentrations and isotope ratios in groundwater studies, we have developed an efficient and portable sampling device using a commercially available membrane contactor. The device separates dissolved gases from a stream of water and collects them in a small copper tube (6 mm in diameter and 100 mm in length with two pinch-off clamps) for noble gas analysis by mass spectrometry. We have examined the performance of the sampler using a tank of homogeneous water prepared in the laboratory and by field testing. We find that our sampling device can extract heavier noble gases (Ar, Kr, and Xe) more efficiently than the lighter ones (He and Ne). An extraction time of about 60 min at a flow rate of 3 L/min is sufficient for all noble gases extracted in the sampler to attain equilibrium with the dissolved phase. The extracted gas sample did not indicate fractionation of helium ((3) He/(4) He) isotopes or other noble gas isotopes. Field performance of the sampling device was tested using a groundwater well in Vienna and results were in excellent agreement with those obtained from the conventional copper tube sampling method., (© 2012, National Ground Water Association.)

Helium direct analysis in real time (He-DART) mass spectrometry (MS) analysis of labile compounds usually tends to be challenging because of the occurrence of prominent fragmentation, which obscures the assigning of an ion to an independent species or merely a fragment in a mixture. In the present work, argon DART (Ar-DART) MS in conjunction with makeup solvents has been demonstrated to analyze a variety of labile compounds including nucleosides, alkaloids, glucose, and other small molecules. The results presented here confirm that Ar-DART can generate significantly less energetic ions than conventional He-DART and is able to produce the intact molecular ions with little or no fragmentation in both positive and negative ion modes. Adding a makeup solvent (absolute ethyl alcohol, methanol, fluorobenzene, or acetone) to the argon gas stream at the exit of the DART ion source can result in 1-2 orders of magnitude increase in detection signals. The sensitivity attainable by Ar-DART was found to be comparable to that by He-DART. The investigation of influence of solvents improves our understanding of the fundamental desorption and ionization processes in DART. The practical application of this rapid and high throughput method is demonstrated by the successful analysis of a natural product (Crude Kusnezoff Monkshood) extract, demonstrating the great potential in mixture research.

Reliably identifying the effects of energy development on groundwater quality can be difficult because baseline assessments of water quality completed before the onset of energy development are rare and because interactions between hydrocarbon reservoirs and aquifers can be complex, involving both natural and human processes. Groundwater age and mixing data can strengthen interpretations of monitoring data from those areas by providing better understanding of the groundwater flow systems. Chemical, isotopic, and age tracers were used to characterize groundwater ages and mixing with deeper saline water in three areas of the Piceance Basin natural gas province. The data revealed a complex array of groundwater ages (<10 to >50,000 years) and mixing patterns in the basin that helped explain concentrations and sources of methane in groundwater. Age and mixing data also can strengthen the design of monitoring programs by providing information on time scales at which water quality changes in aquifers might be expected to occur. This information could be used to establish maximum allowable distances of monitoring wells from energy development activity and the appropriate duration of monitoring.

The objective of the study was to evaluate the different headspace equilibration methods for the quantification of dissolved greenhouse gases in groundwater. Groundwater samples were collected from wells with contrasting hydrogeochemical properties and degassed using the headspace equilibration method. One hundred samples from each well were randomly selected, treatments were applied and headspace gases analysed by gas chromatography. Headspace equilibration treatments varied helium (He):water ratio, shaking time and standing time. Mean groundwater N(2)O, CO(2) and CH(4) concentrations were 0.024 mg N L(-1), 13.71 mg C L(-1) and 1.63 μg C L(-1), respectively. All treatments were found to significantly influence dissolved gas concentrations. Considerable differences in the optimal He:water ratio and standing time were observed between the three gases. For N(2)O, CO(2) and CH(4) the optimum operating points for He:water ratio was 4.4:1, 3:1 and 3.4:1; shaking time was 13, 12 and 13 min; and standing time was 63, 17 and 108 min, respectively. The headspace equilibration method needs to be harmonised to ensure comparability between studies. The experiment reveals that He:water ratio 3:1 and shaking time 13 min give better estimation of dissolved gases than any lower or higher ratios and shaking times. The standing time 63, 17 and 108 min should be applied for N(2)O, CO(2) and CH(4), respectively., (Copyright © 2012. Published by Elsevier Ltd.)

Introduction: Recently developed prototypes of zirconium dioxide and NASICON-based micro solid-state electrolyte oxygen (O2) and carbon dioxide (CO2) sensors were tested for their potential suitability in rebreathers. The O2 sensor has a quasi-indefinite lifetime, whilst that of the CO2 sensor is approximately 700 h. This is a preliminary report of a new technological application., Methods: The O2 sensor was tested in a small pressure chamber to a partial pressure of oxygen (PO2) of 405 kPa (4 bar). The CO2 sensor was tested up to 10 kPa CO2. The response times to a step change of pressure were measured, and cross-sensitivity for helium tested using trimix. A rebreather mouthpiece was modified so that breath-by-breath gas recordings could be observed. Power consumption to heat the sensors was measured., Results: The O2 sensor demonstrated non-linearity, particularly above 101.3 kPa (1 bar) PO2, whereas the output of the CO2 sensor showed an inverse logarithmic relationship. Cross-sensitivity to helium was observed. The mean t90 response times were 90 (SD 10) ms for the O2 sensor, and 100 (SD 10) ms for the CO2 sensor. Breath-by-breath recordings showed slight damping of the CO2 trace due to electronic filtering. Power consumption was 1.5-2 W per sensor., Conclusions: The fast response times would allow accurate breath-by-breath measurement. Even though the O2 sensor has a non-linear response, measurement is possible using multi-point calibration. Further design is necessary to allow trimix to be used as the diluent. A major disadvantage is the high power consumption needed to heat the sensors to high temperatures.

Background: Small airway disease frequently occurs in chronic lung diseases and may cause ventilation inhomogeneity (VI), which can be assessed by washout tests of inert tracer gas. Using two tracer gases with unequal molar mass (MM) and diffusivity increases specificity for VI in different lung zones. Currently washout tests are underutilised due to the time and effort required for measurements. The aim of this study was to develop and validate a simple technique for a new tidal single breath washout test (SBW) of sulfur hexafluoride (SF(6)) and helium (He) using an ultrasonic flowmeter (USFM)., Methods: The tracer gas mixture contained 5% SF(6) and 26.3% He, had similar total MM as air, and was applied for a single tidal breath in 13 healthy adults. The USFM measured MM, which was then plotted against expired volume. USFM and mass spectrometer signals were compared in six subjects performing three SBW. Repeatability and reproducibility of SBW, i.e., area under the MM curve (AUC), were determined in seven subjects performing three SBW 24 hours apart., Results: USFM reliably measured MM during all SBW tests (n = 60). MM from USFM reflected SF(6) and He washout patterns measured by mass spectrometer. USFM signals were highly associated with mass spectrometer signals, e.g., for MM, linear regression r-squared was 0.98. Intra-subject coefficient of variation of AUC was 6.8%, and coefficient of repeatability was 11.8%., Conclusion: The USFM accurately measured relative changes in SF(6) and He washout. SBW tests were repeatable and reproducible in healthy adults. We have developed a fast, reliable, and straightforward USFM based SBW method, which provides valid information on SF(6) and He washout patterns during tidal breathing.

This work aims to measure different components of natural background radiation on a train. A radiation measurement system consisting of four types of radiation detectors, namely, a Berkeley Lab cosmic-ray detector, moderated (3)He detector, high-pressure ionisation chamber and NaI(Tl) spectrometer, associated with a global positioning system unit was established for this purpose. For the commissioning of the system, a test measurement on a train along the railway around the northern Taiwan coast from Hsinchu to Hualien with a distance of ∼ 275 km was carried out. No significant variation of the intensities of the different components of natural background radiation was observed, except when the train went underground or in the tunnels. The average external dose rate received by the crew of the train was estimated to be 62 nSv h(-1).

The south east basin of France shelters deep CO₂ reservoirs often studied with the aim of better constraining geological CO₂ storage operations. Here we present new soil gas data, completing an existing dataset (CO₂, ²²²Rn, ⁴He), together with mineralogical and physical characterisations of soil columns, in an attempt to better understand the spatial distribution of gas concentrations in the soils and to rule on the sealed character of the CO₂ reservoir at present time. Anomalous gas concentrations were found but did not appear to be clearly related to geological structures that may drain deep gases up to the surface, implying a dominant influence of near surface processes as indicated by carbon isotope ratios. Coarse grained, quartz-rich soils favoured the existence of high CO₂ concentrations. Fine grained clayey soils preferentially favoured the existence of ²²²Rn but not CO₂. Soil formations did not act as barriers preventing gas migrations in soils, either due to water content or due to mineralogical composition. No abundant leakage from the Montmiral reservoir can be highlighted by the measurements, even near the exploitation well. As good correlation between CO₂ and ²²²Rn concentrations still exist, it is suggested that ²²²Rn migration is also CO₂ dependent in non-leaking areas--diffusion dominated systems., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

We report the first inert gas sensing and characterization studies based on high-resolution localized surface plasmon resonance (HR-LSPR) spectroscopy. HR-LSPR was used to detect the extremely small changes (<3 × 10(-4)) in bulk refractive index when the gas was switched between He(g) and Ar(g) or He(g) and N2(g). We also demonstrate submonolayer sensitivity to adsorbed water from exposure of the sensor to air (40% humidity) versus dry N2(g). These measurements significantly expand the applications space and characterization tools for plasmonic nanosensors.

The Pechelbronn oilfield (Rhine Graben, France), where mining activity ended in the 1960s, has been used for waste disposal for twenty years. Since the wastes are varied, work is underway to identify the discharged materials and their derivatives, as well as to locate and quantify potential discharge sites. Two major goals were assigned to the present work. The first was to identify or refine the location of hidden structures that could facilitate gas emanation up to the surface, by studying soil gas concentrations (mainly (222)Rn, CO(2), CH(4) and helium) and carbon isotope ratios in the CO(2) phase. The second was devoted to examining, from a health and safety viewpoint, if the use of the oilfield as a waste disposal site might have led to enhanced or modified gas emanation throughout the area. It appeared that CO(2) and (222)Rn evolution in the whole area were similar, except near some of the faults and fractures that are known through surface mapping and underground observations. These (222)Rn and CO(2) anomalies made it possible to highlight more emissive zones that are either related to main faults or to secondary fractures acting as migration pathways. In that sense, the CO(2) phase can be used to evaluate (222)Rn activities distant from tectonic structures but can lead to erroneous evaluations near to gas migration pathways. Dumping of wastes, as well as oil residues, did not appear to have a strong influence on soil gaseous species and emanation. Similarly, enhanced gas migration due to underground galleries and exploitation wells has not been established. Carbon isotope ratios suggested a balance of biological phenomena, despite the high CO(2) contents reached. Other monitored gaseous species (N(2), Ar, H(2) and alkanes), when detected, always showed amounts close to those found subsurface and/or in atmospheric gases., (Copyright 2010 Elsevier Ltd. All rights reserved.)

(3)H-(3)He measurements constitute a well-established method for the determination of the residence time of young groundwater. However, this method has rarely been applied to karstified aquifers and in particular to drip water in caves, despite the importance of the information which may be obtained. Besides the determination of transfer times of climate signals from the atmosphere through the epikarst to speleothems as climate archives, (3)H-(3)He together with Ne, Ar, Kr, Xe data may also help to give new insights into the local hydrogeology, e.g. the possible existence of a perched aquifer above a cave. In order to check the applicability of (3)H-(3)He dating to cave drips, we collected drip water samples from three adjacent caves in northwestern Germany during several campaigns. The noble gas data were evaluated by inverse modelling to obtain recharge temperature and excess air, supporting the calculation of the tritiogenic (3)He and hence the (3)H-(3)He age. Although atmospheric noble gases were often found to be close to equilibrium with the cave atmosphere, several drip water samples yielded an elevated (3)He/(4)He ratio, providing evidence for the accumulation of (3)He from the decay of (3)H. No significant contribution of radiogenic (4)He was found, corresponding to the low residence times mostly in the range of one to three years. Despite complications during sampling, conditions of a perched aquifer could be confirmed by replicate samples at one drip site. Here, the excess air indicator ΔNe was about 10 %, comparable to typical values found in aquifers in mid-latitudes. The mean (3)H-(3)He age of 2.1 years at this site presumably refers to the residence time in the perched aquifer and is lower than the entire transit time of 3.4 years estimated from the tritium data.