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We developed a portable mass spectrometric system ("miniRuedi") for quantificaton of the partial pressures of He, Ne (in dry gas), Ar, Kr, N2, O2, CO2, and CH4 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. [ABSTRACT FROM AUTHOR]

Radon (Ran) is a naturally occurring radioactive noble gas, which is ubiquitous in soil gas. Especially, its long-lived isotope 222 (half-life: 3.82 d) gained widespread acceptance as a tracer for gas transport in soils, while the shortlived 220Rn (half-life: 55.6 s) found less interest in environmental studies. However, in some cases, the application of 222 as a tracer in soil gas is complex as its concentrations can be influenced by changes of the transport conditions or of the 220 production of the soil material. Due to the different half-lives of 220Rn and 222, the distances that can be traveled by the respective isotopes before decay differ significantly, with 220Rn migrating over much shorter distances than 222. Therefore, the soil gas concentrations of 220 and 222 are influenced by processes on different length scales. In laboratory experiments in a sandbox, we studied the different transport behaviors or 220 and 222 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 220Rn and 222 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 220Rn and 222 in soil gas for the first time and showed the feasibility of this approach to characterize soil gas transport processes. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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, N2, and O2) 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, N2, and O2 in air-saturated water. The detection limits are below 3 × 10-9 cmSTP3/g for the noble gases and below 400 × 10-9 cmSTP3/g for N2 and O2. 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. [ABSTRACT FROM AUTHOR]

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.

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 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.