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Trees transport gases from below ground into the atmosphere through the process of transpiration. Tracing gases transported through this mechanism continuously and under field conditions remains an experimental challenge. Here we measured gases dissolved in tree sap in-situ and in real time, aiming to simultaneously analyse the transport of several gases (He, Ar, Kr, N2, O2, CO2) from the soil, through the trees, into the atmosphere. We constructed and inserted custom-made semi-permeable membrane probes in the xylem of a fir tree and measured gas abundances at different heights using a portable gas equilibrium membrane-inlet mass spectrometer ('miniRUEDI'). With this method we were able to continuously measure the abundances of He, Ar, Kr, N2, O2, CO2 in sap over several weeks. We observed diurnal variations of CO2 and O2 concentrations that reflected tree physiological activities. As a proof of concept that trees do uptake dissolved gases in soil water, we irrigated the tree with He-enriched water in a tracer experiment, and were able to determine upwards sap flow velocity. Measurements of inert gases together with reactive species as CO2 and O2 allows to separate physical transport and exchange of gases derived from the soil or the atmosphere from biological reactions. We discuss the opportunities that our technique provides for continuous in-situ measurements of gases in tree sap., (© The Author(s) 2024. Published by Oxford University Press.)

Surface water (SW) - groundwater (GW) interactions exhibit complex spatial and temporal patterns often studied using tracers. However, most natural and artificial tracers have limitations in studying SW-GW interactions, particularly if no significant contrasts in concentrations between SW and GW exist or can be maintained for long durations. In such context, (noble) gases have emerged as promising alternatives to add to the available tracer methods, especially with the recent development of portable mass spectrometers, which enable continuous monitoring of dissolved gas concentrations directly in the field. However, long-duration gas injection into river water presents logistical challenges. To overcome this limitation, we present an efficient and robust diffusion-injection apparatus for labeling large amounts of river water. Our setup allows fine, real-time control of the gas injection rate, and is suitable for extended injection durations and different gas species. To illustrate the effectiveness of our approach, we present a case study where helium (He) is used as an artificial tracer to study river water infiltration into an alluvial aquifer. Our injection of He as a tracer increased the dissolved He concentration of the river water by one order of magnitude compared to air-saturated water concentration for 35 days. This experiment yields valuable information on travel times from the river to a pumping well and on the mixing ratios between freshly infiltrated river water and regional groundwater., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The extent of littoral influence on lake gas dynamics remains debated in the aquatic science community due to the lack of direct quantification of lateral gas transport. The prevalent assumption of diffusive horizontal transport in gas budgets fails to explain anomalies observed in pelagic gas concentrations. Here, we demonstrate through high-frequency measurements in a eutrophic lake that daily convective horizontal circulation generates littoral-pelagic advective gas fluxes one order of magnitude larger than typical horizontal fluxes used in gas budgets. These lateral fluxes are sufficient to redistribute gases at the basin-scale and generate concentration anomalies reported in other lakes. Our observations also contrast the hypothesis of pure, nocturnal littoral-to-pelagic exchange by showing that convective circulation transports gases such as oxygen and methane toward both the pelagic and littoral zones during the daytime. This study challenges the traditional pelagic-centered models of aquatic systems by showing that convective circulation represents a fundamental lateral transport mechanism to be integrated into gas budgets.

The sealing characteristics of the geological formation located above a CO 2 storage reservoir, the so-called caprock, are essential to ensure efficient geological carbon storage. If CO 2 were to leak through the caprock, temporal changes in fluid geochemistry can reveal fundamental information on migration mechanisms and induced fluid-rock interactions. Here, we present the results from a unique in-situ injection experiment, where CO 2 -enriched fluid was continuously injected in a faulted caprock analogue. Our results show that the CO 2 migration follows complex pathways within the fault structure. The joint analysis of noble gases, ion concentrations and carbon isotopes allow us to quantify mixing between injected CO 2 -enriched fluid and resident formation water and to describe the temporal evolution of water-rock interaction processes. The results presented here are a crucial complement to the geophysical monitoring at the fracture scale highlighting a unique migration of CO 2 in fault zones., (© 2023. Springer Nature Limited.)

The quantification of carbon cycling across the groundwater-stream-atmosphere continuum (GSAC) is crucial for understanding regional and global carbon cycling. However, this quantification remains challenging due to highly coupled carbon exchange and turnover in the GSAC. Here, we disentangled carbon cycling processes in a representative groundwater-stream-atmosphere transect by obtaining and numerically simulating high-resolution time series of dissolved He, Ar, Kr, O 2 , CO 2 , and CH 4 concentrations. The results revealed that groundwater contributed ∼60% of CO 2 and ∼30% of CH 4 inputs to the stream, supporting stream CO 2 and CH 4 emissions to the atmosphere. Furthermore, diurnal variations in stream metabolism (-0.6 to 0.6 mol O 2 m -2 day -1 ) induced pronounced carbonate precipitation during the day and dissolution at night. The significant diurnal variability of biogeochemical processes emphasizes the importance of high-resolution time series investigations of carbon dynamics. This study shows that dissolved gases are promising environmental tracers for discerning and quantifying carbon cycling across the GSAC with high spatiotemporal resolution. Our high-resolution carbon exchange and turnover quantification provides a process-oriented and mechanistic understanding of carbon cycling across the GSAC.

Known locally as the water mountain, for millennia Japan's iconic Mt Fuji has provided safe drinking water to millions of people via a vast network of groundwater and freshwater springs. Groundwater, which is recharged at high elevations, flows down Fuji's flanks within three basaltic aquifers, ultimately forming countless pristine freshwater springs among Fuji's foothills. Here we challenge the current conceptual model of Fuji being a simple system of laminar groundwater flow with little to no vertical exchange between its three aquifers. This model contrasts strongly with Fuji's extreme tectonic instability due to its unique location on top of the only known continental trench-trench-trench triple junction, its complex geology and its unusual microbial spring water communities. On the basis of a unique combination of microbial environmental DNA, vanadium and helium tracers, we provide evidence for prevailing deep circulation and a previously unknown deep groundwater contribution to Fuji's freshwater springs. The most substantial deep groundwater upwelling has been found along Japan's most tectonically active region, the Fujikawa-kako Fault Zone. Our findings broaden the hydrogeological understanding of Fuji and demonstrate the vast potential of combining environmental DNA, on-site noble gas and trace element analyses for groundwater science., Competing Interests: Competing interestsThe authors declare no competing interests., (© The Author(s) 2023.)

Groundwater contamination of geogenic arsenic (As) remains a global health threat, particularly in south-east Asia. The prominent correlation often observed between high As concentrations and methane (CH 4 ) stimulated the analysis of the gas dynamics in an As contaminated aquifer, whereby noble and reactive gases were analysed. Results show a progressive depletion of atmospheric gases (Ar, Kr and N 2 ) alongside highly increasing CH 4 , implying that a free gas phase comprised mainly of CH 4 is formed within the aquifer. In contrast, Helium (He) concentrations are high within the CH 4 (gas) producing zone, suggesting longer (groundwater) residence times. We hypothesized that the observed free (CH 4 ) gas phase severely detracts local groundwater (flow) and significantly reduces water renewal within the gas producing zone. Results are in-line with this hypothesis, however, a second hypothesis has been developed, which focuses on the potential transport of He from an adjacent aquitard into the (CH 4 ) gas producing zone. This second hypothesis was formulated as it resolves the particularly high He concentrations observed, and since external solute input from the overlying heterogeneous aquitard cannot be excluded. The proposed feedback between the gas phase and hydraulics provides a plausible explanation of the anti-intuitive correlation between high As and CH 4 , and the spatially highly patchy distribution of dissolved As concentrations in contaminated aquifers. Furthermore, the increased groundwater residence time would allow for the dissolution of more crystalline As-hosting iron(Fe)-oxide phases in conjunction with the formation of more stable secondary Fe minerals in the hydraulically-slowed (i.e., gas producing) zone; a subject which calls for further investigation., (Copyright © 2022. Published by Elsevier Ltd.)

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 miniRUEDI is a portable mass spectrometer system designed for on-site analysis of gases in the environment during field work and at remote locations. For many gas species (e.g., He, Ar, Kr, N 2 , O 2 , CO 2 ) the ion-current peak-heights measured with the mass spectrometer can usually be calibrated in terms of the partial pressures by simple peak-height comparison relative to a gas standard with well known partial pressures. However, depending on the composition of the analysed gases, the ion currents measured at certain m / z ratios may result from overlapping signals of multiple species (for example CH 4 , O 2 and N 2 at m / z = 15 and 16; or Ne, Ar and H 2 O at m / z = 20 ). Here, we present a method extension to the existing miniRUEDI peak-height comparison in order to resolve such overlap interferences: • We developed and tested a data processing procedure for accurate deconvolution and compensation of such mass-spectrometric overlap interferences. • The method was incorporated into the miniRUEDI open-source software (ruediPy). • The method substantially improves the analytical accuracy in situations where mass-spectrometric interferences cannot be avoided., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2020 The Author(s).)

Temporal changes in groundwater chemistry can reveal information about the evolution of flow path connectivity during crustal deformation. Here, we report transient helium and argon concentration anomalies monitored during a series of hydraulic reservoir stimulation experiments measured with an in situ gas equilibrium membrane inlet mass spectrometer. Geodetic and seismic analyses revealed that the applied stimulation treatments led to the formation of new fractures (hydraulic fracturing) and the reactivation of natural fractures (hydraulic shearing), both of which remobilized (He, Ar)-enriched fluids trapped in the rock mass. Our results demonstrate that integrating geochemical information with geodetic and seismic data provides critical insights to understanding dynamic changes in fracture network connectivity during reservoir stimulation. The results of this study also shed light on the linkages between fluid migration, rock deformation and seismicity at the decameter scale.

The spatiotemporal dynamics of denitrification in groundwater are still not well-understood because of a lack of efficient methods to quantify this biogeochemical reaction pathway. Previous research used the ratio of N 2 to argon (Ar) to quantify net production of N 2 via denitrification by separating the biologically generated N 2 component from the atmospheric-generated components. However, this method does not allow the quantification of the atmospheric components accurately because the differences in gas partitioning between N 2 and Ar are being neglected. Moreover, conventional (noble) gas analysis in water is both expensive and labor-intensive. We overcome these limitations by using a portable mass spectrometer system, which enables a fast and efficient in situ analysis of dissolved (noble) gases in groundwater. By analyzing a larger set of (noble) gases (N 2 , He, Ar, and Kr) combined with a physically meaningful excess air model, we quantified N 2 originating from denitrification. Consequently, we were able to study the spatiotemporal dynamics of N 2 production due to denitrification in riparian groundwater over a six-month period. Our results show that denitrification is highly variable in space and time, emphasizing the need for spatially and temporally resolved data to accurately account for denitrification dynamics in groundwater.

This study presents a novel data set of noble gas compositions and 3 H/ 3 He measurements in groundwater samples from the Gardermoen Aquifer in Norway. The motivation was to test the applicability of noble gases as tracers in constraining the conceptual model and improve the understanding of deeper parts of the aquifer. Flow models have been used as tools for water resource management at the Oslo international airport, which is located within the aquifer recharge area, and bordering towards protected nature reserves. Current models are well calibrated for upper parts of the aquifer, and in line with new noble gas data. However, in some areas large inverse pressure gradients are observed. Interpretation of noble gas data proved useful in understanding these pressure deviations as a result of water retention in low permeability layers of clay and silt. Noble gas composition, isotopic ratios and tritium water ages define different water "types". Mixing along flow path or as a consequence of pumping were found to be indicators of geological heterogeneity, and were used to evaluate degree of flow separation as well as vertical versus horizontal flux. 3 H/ 3 He water ages varied between 0 and 50 years, increasing with depth below the groundwater table and along flow paths. These data indicate lower vertical permeability and longer residence times in deeper parts of the aquifer than suggested by previous models. This study is of high relevance in the continued water resource management scheme at Gardermoen, for improving existing models and in sound, long-term monitoring of groundwater, ensuring sustained influx towards sensitive biotopes., (Copyright © 2018. Published by Elsevier B.V.)

The estimation of gas-exchange rates between streams and the atmosphere is of great importance for the fate of volatile compounds in rivers. For dissolved oxygen, this exchange process is called reaeration, and its accurate and precise estimation is essential for the quantification of metabolic rates. A common method for the determination of gas-exchange rates is through artificial gas-tracer tests with a proxy gas. We present the implementation of a portable gas-equilibrium membrane inlet mass spectrometer (GE-MIMS) to record concentrations of krypton and propane injected as tracer compound in the context of a gas-tracer test. The field-compatible GE-MIMS uses signals of atmospheric measurements for concentration standardization, and allows recording the dissolved-gas concentrations at a high temporal resolution, leading to overall low measurement uncertainty. Furthermore, the in-situ approach avoids loss of gas during the steps of sampling, transport, storage, and analysis required for ex-situ gas measurements. We compare obtained gas-exchange rate coefficients, reaeration and derived metabolic rates from the in-situ measurements to results obtained from head-space sampling of propane followed by laboratory analysis, and find much lower uncertainties with the in-situ method., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Gas exchange across the air-water interface is a key process determining the release of greenhouse gases from surface waters and a fundamental component of gas dynamics in aquatic systems. To experimentally quantify the gas transfer velocity in a wide range of aquatic settings, a novel method based on recently developed techniques for the in situ, near-continuous measurement of dissolved (noble) gases with a field portable mass spectrometer is presented. Variations in observed dissolved gas concentrations are damped and lagged with respect to equilibrium concentrations, being the result of (a) temperature (and thus solubility) variations, (b) water depth, and (c) the specific gas transfer velocity ( k i ). The method fits a model to the measured gas concentrations to derive the gas transfer velocity from the amplitude and the phase lag between observed and equilibrium concentrations. With the current experimental setup, the method is sensitive to gas transfer velocities of 0.05-9 m/day (for N 2 ), at a water depth of 1 m, and a given daily water temperature variation of 10 °C. Experiments were performed (a) in a controlled experiment to prove the concept and to confirm the capability to determine low transfer velocities and (b) in a field study in a shallow coastal lagoon covering a range of transfer velocities, demonstrating the field applicability of the method.

Atmospheric noble gases are routinely used as natural tracers to analyze gas transfer processes in aquatic systems. Their isotopic ratios can be employed to discriminate between different physical transport mechanisms by comparison to the unfractionated atmospheric isotope composition. In many applications of aquatic systems molecular diffusion was thought to cause a mass dependent fractionation of noble gases and their isotopes according to the square root ratio of their masses. However, recent experiments focusing on isotopic fractionation within a single element challenged this broadly accepted assumption. The determined fractionation factors of Ne, Ar, Kr and Xe isotopes revealed that only Ar follows the prediction of the so-called square root relation, whereas within the Ne, Kr and Xe elements no mass-dependence was found. The reason for this unexpected divergence of Ar is not yet understood. The aim of our computational exercise is to establish the molecular-resolved mechanisms behind molecular diffusion of noble gases in water. We make the hypothesis that weak intermolecular interactions are relevant for the dynamical properties of noble gases dissolved in water. Therefore, we used ab initio molecular dynamics to explicitly account for the electronic degrees of freedom. Depending on the size and polarizability of the hydrophobic particles such as noble gases, their motion in dense and polar liquids like water is subject to different diffusive regimes: the inter-cavity hopping mechanism of small particles (He, Ne) breaks down if a critical particle size achieved. For the case of large particles (Kr, Xe), the motion through the water solvent is governed by mass-independent viscous friction leading to hydrodynamical diffusion. Finally, Ar falls in between the two diffusive regimes, where particle dispersion is propagated at the molecular collision time scale of the surrounding water molecules.

In closed-basin lakes, sediment porewater salinity can potentially be used as a conservative tracer to reconstruct past fluctuations in lake level. However, until now, porewater salinity profiles did not allow quantitative estimates of past lake-level changes because, in contrast to the oceans, significant salinity changes (e.g., local concentration minima and maxima) had never been observed in lacustrine sediments. Here we show that the salinity measured in the sediment pore water of Lake Van (Turkey) allows straightforward reconstruction of two major transgressions and a major regression that occurred during the last 250 ka. We observed strong changes in the vertical salinity profiles of the pore water of the uppermost 100 m of the sediments in Lake Van. As the salinity balance of Lake Van is almost at steady-state, these salinity changes indicate major lake-level changes in the past. In line with previous studies on lake terraces and with seismic and sedimentological surveys, we identify two major transgressions of up to +105 m with respect to the current lake level at about 135 ka BP and 248 ka BP starting at the onset of the two previous interglacials (MIS5e and MIS7), and a major regression of about -200 m at about 30 ka BP during the last ice age.

We developed a portable mass spectrometric system ("miniRuedi") for quantificaton of the partial pressures of He, Ne (in dry gas), Ar, Kr, N 2 , O 2 , CO 2 , and CH 4 in gaseous and aqueous matrices in environmental systems with an analytical uncertainty of 1-3%. The miniRuedi does not require any purification or other preparation of the sampled gases and therefore allows maintenance-free and autonomous operation. The apparatus is most suitable for on-site gas analysis during field work and at remote locations due to its small size (60 cm × 40 cm × 14 cm), low weight (13 kg), and low power consumption (50 W). The gases are continuously sampled and transferred through a capillary pressure reduction system into a vacuum chamber, where they are analyzed using a quadrupole mass spectrometer with a time resolution of ≲1 min. The low gas consumption rate (<0.1 mL/min) minimizes interference with the natural mass balance of gases in environmental systems, and allows the unbiased quantification of dissolved-gas concentrations in water by gas/water equilibration using membrane contractors (gas-equilibrium membrane-inlet mass spectrometry, GE-MIMS). The performance of the miniRuedi is demonstrated in laboratory and field tests, and its utility is illustrated in field applications related to soil-gas formation, lake/atmosphere gas exchange, and seafloor gas emanations.

There is conclusive evidence that the methods most commonly used to sample methane (CH4) dissolved in the pore water of lake sediments produce results that are likely to be affected by gas loss or gas exchange with the atmosphere. To determine the in situ amount of CH4 per unit mass of pore water in sediments, we developed and validated a new method that combines techniques developed for noble-gas analysis in pore waters with a standard headspace technique to quantify the CH4 present in the pore space in dissolved and gaseous form. The method was tested at two sites: Lake Lungern, where CH4 concentrations were close to saturation; and Lake Rotsee, where CH4 concentrations are known to exceed saturation and where CH4 bubble formation and gas ebullition are commonly observed. We demonstrate that the new method, in contrast to the available methods, more reliably captures the total amount of CH4 per unit mass of pore water consisting of both dissolved and free CH4 (i.e., gas bubbles) in the pore space of the sediment.

Rationale: Oxygen isotope fractionation of molecular O2 is an important process for the study of aerobic metabolism, photosynthesis, and formation of reactive oxygen species. The latter is of particular interest for investigating the mechanism of enzyme-catalyzed reactions, such as the oxygenation of organic pollutants, which is an important detoxification mechanism., Methods: We developed a simple method to measure the δ(18) O values of dissolved O2 in small samples using automated split injection for gas chromatography coupled to isotope ratio mass spectrometry (GC/IRMS). After creating a N2 headspace, the dissolved O2 partitions from aqueous solution to the headspace, from which it can be injected into the gas chromatograph., Results: In aqueous samples of 10 mL and in diluted air samples, we quantified the δ(18) O values at O2 concentrations of 16 μM and 86 μM, respectively. The chromatographic separation of O2 and N2 with a molecular sieve column made it possible to use N2 as the headspace gas for the extraction of dissolved O2 from water. We were therefore able to apply a rigorous δ(18) O blank correction for the quantification of (18) O/(16) O ratios in 20 nmol of injected O2 ., Conclusions: The successful quantification of (18) O-kinetic isotope effects associated with enzymatic and chemical reduction of dissolved O2 illustrates how the proposed method can be applied for studying enzymatic O2 activation mechanisms in a variety of (bio)chemical processes., (Copyright © 2016 John Wiley & Sons, Ltd.)

Although the naturally occurring atmospheric noble gases He, Ne, Ar, Kr, and Xe possess great potential as tracers for studying gas exchange in living beings, no direct analytical technique exists for simultaneously determining the absolute concentrations of these noble gases in body fluids in vivo. In this study, using human blood as an example, the absolute concentrations of all stable atmospheric noble gases were measured simultaneously by combining and adapting two analytical methods recently developed for geochemical research purposes. The partition coefficients determined between blood and air, and between blood plasma and red blood cells, agree with values from the literature. While the noble-gas concentrations in the plasma agree rather well with the expected solubility equilibrium concentrations for air-saturated water, the red blood cells are characterized by a distinct supersaturation pattern, in which the gas excess increases in proportion to the atomic mass of the noble-gas species, indicating adsorption on to the red blood cells. This study shows that the absolute concentrations of noble gases in body fluids can be easily measured using geochemical techniques that rely only on standard materials and equipment, and for which the underlying concepts are already well established in the field of noble-gas geochemistry.

In recent years, mass spectrometers with a membrane inlet separating gases from water for final analysis have been used successfully for the on-site quantification of dissolved gases in surface waters. In 'classical' membrane inlet mass spectrometers (MIMS), the membrane directly separates the water from the high-vacuum environment of the mass spectrometer. The gas equilibrium MIMS (GE-MIMS) that is described in this review, however, makes use of an intermediate pressure reduction stage after the membrane inlet. Hence, the gas concentrations after the membrane are at steady state, near solubility equilibrium with the water to be analyzed. This setup has several advantages over classical MIMS, which enable autonomous and continuous in-field operation. The GE-MIMS can be used to acquire noble gas concentration time series (NGTS). Noble gases are useful tracers for physical gas exchange and transport in groundwater and other aqueous systems. Hence NGTS enable the temporal dynamics of physical gas exchange and transport in groundwater and other aqueous systems to be investigated. To determine the O2 turnover that has occurred in groundwater since recharge, both the O2 concentration in situ and the total input of O2 to the groundwater since recharge is needed. Determination of the latter is only possible if the relevant physical exchange and transport mechanisms can be quantified. In particular, gas exchange between soil air and groundwater often significantly affects groundwater O2 concentrations. Determination of O2 turnover in groundwater therefore requires a combined analysis of O2 and noble gas concentrations.

Radon (Rn) is a naturally occurring radioactive noble gas, which is ubiquitous in soil gas. Especially, its long-lived isotope (222)Rn (half-life: 3.82 d) gained widespread acceptance as a tracer for gas transport in soils, while the short-lived (220)Rn (half-life: 55.6 s) found less interest in environmental studies. However, in some cases, the application of (222)Rn as a tracer in soil gas is complex as its concentrations can be influenced by changes of the transport conditions or of the (222)Rn production of the soil material. Due to the different half-lives of (220)Rn and (222)Rn, the distances that can be traveled by the respective isotopes before decay differ significantly, with (220)Rn migrating over much shorter distances than (222)Rn. Therefore, the soil gas concentrations of (220)Rn and (222)Rn are influenced by processes on different length scales. In laboratory experiments in a sandbox, we studied the different transport behaviors of (220)Rn and (222)Rn resulting from changing the boundary conditions for diffusive transport and from inducing advective gas movements. From the results gained in the laboratory experiments, we propose the combined analysis of (220)Rn and (222)Rn to determine gas transport processes in soils. In a field study on soil gases in the cover soil of a capped landfill we applied the combined analysis of (220)Rn and (222)Rn in soil gas for the first time and showed the feasibility of this approach to characterize soil gas transport processes.

We developed an analytical method for the simultaneous measurement of dissolved He, Ne, Ar, Kr, Xe, SF6, N2, and O2 concentrations in a single water sample. The gases are extracted from the water using a head space technique and are transferred into a vacuum system for purification and separation into different fractions using a series of cold traps. Helium is analyzed using a quadrupole mass spectrometer (QMS). The remaining gas species are analyzed using a gas chromatograph equipped with a mass spectrometer (GC-MS) for analysis of Ne, Ar, Kr, Xe, N2, and O2 and an electron capture detector (GC-ECD) for SF6 analysis. Standard errors of the gas concentrations are approximately 8% for He and 2-5% for the remaining gas species. The method can be extended to also measure concentrations of chlorofluorocarbons (CFCs). Tests of the method in Lake Lucerne (Switzerland) showed that dissolved gas concentrations agree with measurements from other methods and concentrations of air saturated water. In a small artificial pond, we observed systematic gas supersaturations, which seem to be linked to adsorption of solar irradiation in the pond and to water circulation through a gravel bed.

The oxygen dynamics in the hyporheic zone of a peri-alpine river (Thur, Switzerland), were studied through recording and analyzing the concentration time-series of dissolved argon, oxygen, carbon dioxide, and temperature during low flow conditions, for a period of one week. The argon concentration time-series was used to investigate the physical gas dynamics in the hyporheic zone. Differences in the transport behavior of heat and gas were determined by comparing the diel temperature evolution of groundwater to the measured concentration of dissolved argon. These differences were most likely caused by vertical heat transport which influenced the local groundwater temperature. The argon concentration time-series were also used to estimate travel times by cross correlating argon concentrations in the groundwater with argon concentrations in the river. The information gained from quantifying the physical gas transport was used to estimate the oxygen turnover in groundwater after water recharge. The resulting oxygen turnover showed strong diel variations, which correlated with the water temperature during groundwater recharge. Hence, the variation in the consumption rate was most likely caused by the temperature dependence of microbial activity.

We developed a stand-alone system based on a membrane inlet mass spectrometer (MIMS) for measuring dissolved gas concentrations in groundwater under field conditions. The system permits the concentrations of dissolved gases (He, Ar, Kr, N(2), and O(2)) in groundwater to be determined quasi-continuously (every 12 min) with a precision of better than 4% for He and Kr, and with a precision of 1% for Ar, N(2), and O(2) in air-saturated water. The detection limits are below 3 × 10(-9) cm(3)(STP)(g) for the noble gases and below 400 × 10(-9)cm(3)(STP)(g) for N(2) and O(2). The results of a first deployment of the system in the field indicate that changes in the concentration of Ar that result from diel fluctuations of 3°C in the river water temperature were still able to be resolved in groundwater, although the corresponding temperature signal almost vanished.

We developed a method for the vacuum extraction (VacEx) of volatile organic compounds (VOCs) from water samples for ultratrace determinations of carbon isotopic signatures. Our method permits compound-specific stable carbon isotope analysis (CSIA) at VOC concentrations as low as 0.03-1.34 microg/L. VacEx was developed to extract and preconcentrate VOCs for subsequent carbon-CSIA by the standard technique purge-and-trap (P&T) coupled to an isotope-ratio mass spectrometer (IRMS). Even without complete extraction, the delta(13)C signatures of VOCs determined by VacEx-P&T-IRMS were in good agreement (deviation <1 per thousand) with signatures determined by P&T-IRMS. This indicates that VacEx does not cause isotopic discrimination. Limits of quantification (LOQs) for delta(13)C analysis were: 0.03-0.06 microg/L for benzene, toluene, o-xylene, m-p-xylene and ethylbenzene, 0.09 microg/L for methyl tert-butyl ether (MTBE), and 0.18-0.27 microg/L for trans-DCE, cis-DCE, TCE and PCE. These are the lowest LOQs reported to date for continuous-flow isotope-ratio determinations using a commercially available and automated system. To our knowledge, analytical protocols adopted from noble gas analysis in water were applied for the first time to determine the isotope composition of organic contaminants. We applied VacEx in a field study to illustrate how the determination of VOC isotopic signatures at very low concentrations opens new avenues in the in situ assessment of these priority groundwater pollutants.

Long-term safety assessments for geological disposal of radioactive waste in Switzerland involve the demonstration that the annual radiation dose to humans due to the potential release of radionuclides from the waste repository into the biosphere will not exceed the regulatory limit of 0.1 mSv. Here, we describe the simple but robust approach used by Nagra (Swiss National Cooperative for the Disposal of Radioactive Waste) to quantify the dose to humans as a result to time-dependent release of radionuclides from the geosphere into the biosphere. The model calculates the concentrations of radionuclides in different terrestrial and aquatic compartments of the surface environment. The fluxes of water and solids within the environment are the drivers for the exchange of radionuclides between these compartments. The calculated radionuclide concentrations in the biosphere are then used to estimate the radiation doses to humans due to various exposure paths (e.g. ingestion of radionuclides via drinking water and food, inhalation of radionuclides, external irradiation from radionuclides in soils). In this paper we also discuss recent new achievements and planned future work.

The contamination of groundwater by geogenic arsenic is the cause of major health problems in south and southeast Asia. Various hypotheses proposing that As is mobilized by the reduction of iron (oxy)hydroxides are now under discussion. One important and controversial question concerns the possibility that As contamination might be related to the extraction of groundwater for irrigation purposes. If As were mobilized by the inflow of re-infiltrating irrigation water rich in labile organic carbon, As-contaminated groundwater would have been recharged after the introduction of groundwater irrigation 20-40 years ago. We used environmental tracer data and conceptual groundwater flow and transport modeling to study the effects of groundwater pumping and to assess the role of reinfiltrated irrigation water in the mobilization of As. Both the tracer data and the model results suggest that pumping induces convergent groundwater flow to the depth of extraction and causes shallow, young groundwater to mix with deep, old groundwater. The As concentrations are greatest at a depth of 30 m where these two groundwater bodies come into contact and mix. There, within the mixing zone, groundwater age significantly exceeds 30 years, indicating that recharge of most of the contaminated water occurred before groundwater irrigation became established in Bangladesh. Hence, at least at our study site, the results call into question the validity of the hypothesis that re-infiltrated irrigation water is the direct cause of As mobilization; however, the tracer data suggest that, at our site, hydraulic changes due to groundwater extraction for irrigation might be related to the mobilization of As.