Search

Labeling groundwater by injecting an artificial tracer is a standard and widely used method to study groundwater flow systems. Noble gases dissolved in groundwater are potentially ideal artificial tracers, as they are not subject to biogeochemical transformations, do not adsorb onto the aquifer matrix, are colorless, and have no negative impact on the quality of groundwater resources. In addition, combining different noble-gas species in multi-tracer tests would allow direct analysis of the spatio-temporal heterogeneity of groundwater flow systems. However, while the handling of noble gases is safe and straightforward for injection into groundwater, conventional methods to analyse dissolved noble gases tend to be impractical for groundwater tracer tests. The sampling and subsequent lab-based analysis of dissolved noble gases are laborious, expensive and time intensive. Therefore, only researchers with access to specialized noble-gas labs have attempted such tracer tests. The recently developed gas-equilibrium membrane-inlet mass spectrometers (GE-MIMS) allow efficient on-site analysis of dissolved gases at high temporal resolution. The GE-MIMS instruments thereby eliminate most of the analytical and logistical constraints of conventional lab-based techniques and therefore provide new opportunities for groundwater tests using artificially injected gases. We used a GE-MIMS to systematically test the applicability of He, Kr, and Xe as artificial groundwater tracers. These gas species were injected into groundwater as Dirac-like pulses at three piezometers located at various locations upstream of a pumping well, where dissolved gas concentrations were continuously monitored with the GE-MIMS instrument. The groundwater travel times observed in these tracer tests ranged from a few hours to several weeks, and were consistent with the groundwater flow field at the experimental test site. Travel times determined from the noble gas tracer tests were also consistent with those obtained traditional dye tracers., Frontiers in Water, 4, ISSN:2624-9375

Global estimates see river deltas and estuaries contributing about equally to CO2 and CH4 emissions as lakes and reservoirs, despite a factor 6 smaller surface area. Assessing the horizontal gradients in dissolved gas concentrations from large river reaches to connecting canals and wetland lakes remains a challenge in many deltaic systems. To elucidate the processes affecting local CO2 and CH4 concentrations in the Romanian part of the Danube Delta, we mapped dissolved O2, N2, He and Ar using a portable gas-equilibration membrane-inlet mass spectrometer (GE-MIMS), along with CO2, CH4, water temperature and conductivity. We measured the concentrations along the aquatic continuum from a small houseboat during two campaigns, in spring and autumn, to capture different hydrological and plant growth conditions. Delta-scale concentration patterns were comparably stable across seasons. Small connecting channels were highly influenced by the riparian wetland, which was strongest in the eastern part of the biosphere reserve. These sites represented the delta’s CO2 and CH4 hotspots and showed clear signs of excess air, i.e., supersaturation of dissolved noble gases with respect to air-saturated water. As the adjacent wetland was permanently inundated, this signal was likely caused by root aeration of Phragmites australis, as opposed to traditional excess air formation via water table fluctuations in the unsaturated zone. The special vegetation setting with reed growing on floating peat coincided with the highest CO2 and CH4 concentrations (>700 μmol/L CO2 and 13 μmol/L CH4, respectively) observed in an adjacent channel. Shallow lakes, on the other hand, were major sites of photosynthetic production with O2 oversaturation reaching up to 150% in spring. The observed deficit in non-reactive gases (He, Ar and N2) indicated that the lakes were affected by O2 ebullition from macrophytes. According to our estimations, this ebullitive flux decreased O2 concentrations by up to 2 mg/L. This study highlights the effect of plant-mediated gas transfer on dissolved gas concentrations and supports recent studies stressing the need to account for ebullitive gas exchange when assessing metabolism parameters from O2 in shallow, productive settings., Frontiers in Environmental Science, 10, ISSN:2296-665X

We present noble gas concentrations and helium isotope ratios measured in the pore fluids of two deep-sea sediment cores taken at the Azores Plateau. Nesingle bondXe concentrations were used to estimate the atmospheric noble gas component within the pore fluids and to then determine the terrigenic helium component. The concentrations of terrigenic 3He indicate the presence of hydrothermal fluids and a mantle He component within the sediment pore space. At both sampling locations, the concentration of terrigenic helium increases with sediment depth. The observed concentration gradients suggest a diffusive transport of He through the sediments. The helium isotope ratio of the source of the terrigenic helium is characterized by a typical mid-ocean ridge basalt (MORB). These results support previous studies suggesting that the pelagic sediments surrounding the Azores host active hydrothermal systems. Our data indicate that the transport of terrigenic helium takes place diffusively over larger areas of the ocean floor, and that the concentration of terrigenic helium in the pelagic sediments increases towards the Mid-Atlantic Ridge and Terceira Rift. The data further suggests that in the Azores region the terrigenic noble gas component is only detectable in the sediment pore fluids and cannot be observed in the overlying bottom water. This highlights the potential of measuring noble gas concentrations and isotope ratios in the sediment column to identify hydrothermal activity in the ocean., Chemical Geology, 608, ISSN:0009-2541, ISSN:1872-6836

The success of geological carbon storage depends on the assurance of permanent containment for injected carbon dioxide (CO2) in the storage formation at depth. One of the critical elements of the safekeeping of CO2 is the sealing capacity of the caprock overlying the storage formation despite faults and/or fractures, which may occur in it. In this work, we present an ongoing injection experiment performed in a fault hosted in clay at the Mont Terri underground rock laboratory (NW Switzerland). The experiment aims to improve our understanding of the main physical and chemical mechanisms controlling (i) the migration of CO2 through a fault damage zone, (ii) the interaction of the CO2 with the neighboring intact rock, and (iii) the impact of the injection on the transmissivity in the fault. To this end, we inject CO2-saturated saline water in the top of a 3 m thick fault in the Opalinus Clay, a clay formation that is a good analog of common caprock for CO2 storage at depth. The mobility of the CO2 within the fault is studied at the decameter scale by using a comprehensive monitoring system. Our experiment aims to close the knowledge gap between laboratory and reservoir scales. Therefore, an important aspect of the experiment is the decameter scale and the prolonged duration of observations over many months. We collect observations and data from a wide range of monitoring systems, such as a seismic network, pressure temperature and electrical conductivity sensors, fiber optics, extensometers, and an in situ mass spectrometer for dissolved gas monitoring. The observations are complemented by laboratory data on collected fluids and rock samples. Here we show the details of the experimental concept and installed instrumentation, as well as the first results of the preliminary characterization. An analysis of borehole logging allows for identifying potential hydraulic transmissive structures within the fault zone. A preliminary analysis of the injection tests helped estimate the transmissivity of such structures within the fault zone and the pressure required to mechanically open such features. The preliminary tests did not record any induced microseismic events. Active seismic tomography enabled sharp imaging the fault zone.

Here we present the results of a first application of a “Combined Vacuum Crushing and Sieving (CVCS)” system to determine past (cave / soil) temperatures from dissolved noble gas concentrations in stalagmite samples grown under ‘cold’ climatic conditions (e.g. close to freezing point of water) during the last glacial-interglacial transition. To establish noble gas temperatures (NGTs) also for stalagmites grown in cold regions, we applied the CVCS system to samples from stalagmite M2 precipitated in the Milandre Cave, located in the Swiss Jura Mountains. The investigated stalagmite M2 covers the Allerød – Younger Dryas – Holocene transitions. Noble gas temperatures are determined by using a new algorithm based on noble gas and water abundances and not from concentrations. Noble gas results indicate annual mean temperatures in the Milandre Cave were 2.2 ± 1.8 °C during the late stages of the Allerød, then dropping to 〖0 〗_((-))^( +) 2.6 °C at the onset of the Younger Dryas. Such temperatures indicate conditions near to the freezing point of water during the first part of the Younger Dryas. During the last part of the Younger Dryas, the temperature increased to 6.3 ± 2.3 °C. No early Holocene temperature could be determined due the non-detectable water abundances in these samples, however one late Holocene sample indicates a cave temperature of 8.7 ± 2.7 °C which is close to the present day annual mean temperature. NGTs estimated for the Allerød – Younger Dryas – Holocene are in good agreement with paleo-temperature reconstructions from geochemical and biological proxies in lake sediments. The observed deviations between the different paleo-temperature reconstructions are minor if the according temperatures are rescaled to annual mean temperatures and are primarily attributed to the chronological tuning of the different records. As in other stalagmites, NGT reconstructions of the recently precipitated stalagmite (‘young’) samples again are biased, most likely due to diffusive gas loss during sample processing. We speculate that a reduced retentivity of noble gases during experimental sample processing is a general feature of recently precipitated stalagmite fabrics. Therefore, the recently precipitated stalagmite samples do not allow the reliable NGT determination given the currently available experimental methods. Nevertheless, this study makes the case that noble gas thermometry can be applied to stalagmites for physically based paleo-temperature reconstruction, also for stalagmites grown during cold climatic conditions.

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.

This paper presents a novel extraction device for water and noble gases from speleothem samples for noble gas paleotemperature determination. The “combined vacuum crushing and sieving (CVCS) system” was designed to reduce the atmospheric noble gas contents from air inclusions in speleothem samples by up to 2 orders of magnitude without adsorbing atmospheric noble gases onto the freshly produced grain surfaces, a process that had often hampered noble gas temperature (NGT) determination in the past. We also present the results from first performance tests of the CVCS system processing stalagmite samples grown at a known temperature. This temperature is reliably reproduced by the NGTs derived from Ar, Kr, and Xe extracted from the samples. The CVCS system is, therefore, suitable for routine determinations of accurate NGTs. In combination with stalagmite dating, these NGTs will allow reconstructing past regional temperature evolutions, and also support the interpretation of the often complex stable isotope records preserved in the stalagmites' calcite.

In this work we present noble-gas concentration profiles measured in the water column and in the sediment pore water of the Earth's largest soda lake: Lake Van (eastern Anatolia, Turkey). The concentrations of noble gases (in particular Ar, Kr, and Xe) in the water body deviate significantly from the expected equilibrium concentrations calculated from the in situ temperature and salinity using existing solubility functions for seawater. The specific chemical composition of the water of the soda lake seems to be responsible for the observed deviations. Our measurements allow the identification and quantification of salinity factors that can be applied to correctly calculate the noble-gas equilibrium concentrations for the lake. These salinity factors provide a solid and robust empirical basis for the interpretation of noble-gas concentration signals measured in the sediment pore water of Lake Van in terms of palaeosalinity and palaeotemperature. (C) 2012 Elsevier Ltd. All rights reserved.

Here we present a new method for the sampling and quantitative extraction of dissolved He, Ne, Ar, Kr, and Xe from lake sediment samples leading to deter- minations of porewater noble gas concentration profiles and the isotopic ratios 3He/4He, 20Ne/22Ne, and 40Ar/36Ar. Bulk sediment is transferred from a sediment core into standard Cu sample tubes without exposure to the atmosphere or other gas reservoirs. The noble gases are then extracted from the porewater by degassing the sediment in an evacuated extraction vessel and analyzed following standard mass spectrometric procedures. In tests of the new method using 0.8 to 1.4 m long sediment cores from two Swiss lakes, analytical uncertainties were only slightly greater than those of standard water samples. The majority of porewater noble gas concentrations and isotopic ratios were found to correspond closely to those measured in the overlying lake water. Because these values reflect water temperature and salinity during atmospheric equilibration at the lake surface, historical conditions are expected to be archived further downcore in the sediment porewater. This method therefore has great potential for paleolimnological reconstructions. The formation of methane bubbles in anoxic sediment layers is one process that may alter gas distributions. However because the lighter noble gases are most sensitive to degassing effects, noble gas data can be used to detect this process. In addition, noble gas data can yield information on the transport processes occurring in the sediment pore space and on the input of water or gas to the sediment from external sources.

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., PLoS ONE, 9 (5), ISSN:1932-6203