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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.

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.

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.

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.

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.

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.