In-situ measurements of dissolved gases in xylem sap as tracers in plant physiology.

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.

Efficient injection of gas tracers into rivers: A tool to study Surface water-Groundwater interactions.

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.

Lake surface cooling drives littoral-pelagic exchange of dissolved gases.

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.

In-situ experiment reveals CO enriched fluid migration in faulted caprock.

The sealing characteristics of the geological formation located above a CO storage reservoir, the so-called caprock, are essential to ensure efficient geological carbon storage. If CO 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-enriched fluid was continuously injected in a faulted caprock analogue.

Quantifying Carbon Cycling across the Groundwater-Stream-Atmosphere Continuum Using High-Resolution Time Series of Multiple Dissolved Gases.

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, CO, and CH concentrations.

Exploring the reliability of Rn as a tracer of groundwater age in alluvial aquifers: Insights from the explicit simulation of variable Rn production.

Knowledge of groundwater residence times (GRT; the time elapsed since surface water infiltration) between losing rivers and pumping wells is crucial for management of water resources in alluvial aquifers. The radioactive noble gas radon-222 (Rn) has been used for decades as a natural indicator of surface water infiltration, as it can provide quantitative information on GRT. However, models using Rn as a tracer of GRT are often based on a set of highly simplifying assumptions, including spatially homogenous Rn production and exclusively advective mass transport within the aquifer.

Revisiting Mt Fuji's groundwater origins with helium, vanadium and environmental DNA tracers.

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.

Hotspots of geogenic arsenic and manganese contamination in groundwater of the floodplains in lowland Amazonia (South America).

Arsenic enrichment in groundwater resources in deltas and floodplains of large sediment-rich rivers is a worldwide natural hazard to human health. High spatial variability of arsenic concentrations in affected river basins limits cost-effective mitigation strategies. Linking the chemical composition of groundwater with the topography and fluvial geomorphology is a promising approach for predicting arsenic pollution on a regional scale.

Noble gas constraints on the fate of arsenic in groundwater.

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) 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) alongside highly increasing CH, implying that a free gas phase comprised mainly of CH is formed within the aquifer.

Carbon and methane cycling in arsenic-contaminated aquifers.

Geogenic arsenic (As) contamination of groundwater is a health threat to millions of people worldwide, particularly in alluvial regions of South and Southeast Asia. Mitigation measures are often hindered by high heterogeneities in As concentrations, the cause(s) of which are elusive. Here we used a comprehensive suite of stable isotope analyses and hydrogeochemical parameters to shed light on the mechanisms in a typical high-As Holocene aquifer near Hanoi where groundwater is advected to a low-As Pleistocene aquifer.

Widespread six degrees Celsius cooling on land during the Last Glacial Maximum.

The magnitude of global cooling during the Last Glacial Maximum (LGM, the coldest multimillennial interval of the last glacial period) is an important constraint for evaluating estimates of Earth's climate sensitivity. Reliable LGM temperatures come from high-latitude ice cores, but substantial disagreement exists between proxy records in the low latitudes, where quantitative low-elevation records on land are scarce. Filling this data gap, noble gases in ancient groundwater record past land surface temperatures through a direct physical relationship that is rooted in their temperature-dependent solubility in water.

Combined method of H/He apparent age and on-site helium analysis to identify groundwater flow processes and transport of perchloroethylene (PCE) in an urban area.

Urban groundwater management requires a thorough and robust scientific understanding of flow and transport processes. H/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.

Deconvolution and compensation of mass spectrometric overlap interferences with the miniRUEDI portable mass spectrometer.

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.

In situ observation of helium and argon release during fluid-pressure-triggered rock deformation.

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.

Spatial and temporal evolution of groundwater arsenic contamination in the Red River delta, Vietnam: Interplay of mobilisation and retardation processes.

Geogenic arsenic (As) contamination of groundwater poses a major threat to global health, particularly in Asia. To mitigate this exposure, groundwater is increasingly extracted from low-As Pleistocene aquifers. This, however, disturbs groundwater flow and potentially draws high-As groundwater into low-As aquifers.

A New in Situ Method for Tracing Denitrification in Riparian Groundwater.

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 to argon (Ar) to quantify net production of N via denitrification by separating the biologically generated N 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 and Ar are being neglected.

Noble gas composition and H/He groundwater ages in the Gardermoen Aquifer, Norway: Improved understanding of flow dynamics as a tool for water management.

This study presents a novel data set of noble gas compositions and H/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.

A Novel Approach To Quantify Air-Water Gas Exchange in Shallow Surface Waters Using High-Resolution Time Series of Dissolved Atmospheric Gases.

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).

Porewater salinity reveals past lake-level changes in Lake Van, the Earth's largest soda lake.

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.

Diverging effects of isotopic fractionation upon molecular diffusion of noble gases in water: mechanistic insights through ab initio molecular dynamics simulations.

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.

A Portable and Autonomous Mass Spectrometric System for On-Site Environmental Gas Analysis.

We developed a portable mass spectrometric system ("miniRuedi") for quantificaton of the partial pressures of He, Ne (in dry gas), Ar, Kr, N, O, CO, and CH 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).

Improved Method for the Quantification of Methane Concentrations in Unconsolidated Lake Sediments.

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.

Forecasting Groundwater Temperature with Linear Regression Models Using Historical Data.

Although temperature is an important determinant of many biogeochemical processes in groundwater, very few studies have attempted to forecast the response of groundwater temperature to future climate warming. Using a composite linear regression model based on the lagged relationship between historical groundwater and regional air temperature data, empirical forecasts were made of groundwater temperature in several aquifers in Switzerland up to the end of the current century. The model was fed with regional air temperature projections calculated for greenhouse-gas emissions scenarios A2, A1B, and RCP3PD.

Determination of natural in vivo noble-gas concentrations in human blood.

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.

Conquering the outdoors with on-site mass spectrometry.

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.