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1.
Tree Physiol ; 2024 Jun 10.
Artículo en Inglés | MEDLINE | ID: mdl-38857369

RESUMEN

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.

2.
Water Res ; 254: 121375, 2024 May 01.
Artículo en Inglés | MEDLINE | ID: mdl-38442605

RESUMEN

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.


Asunto(s)
Agua Subterránea , Contaminantes Químicos del Agua , Ríos , Agua , Monitoreo del Ambiente/métodos , Espectrometría de Masas , Contaminantes Químicos del Agua/análisis
3.
Sci Adv ; 10(4): eadi0617, 2024 Jan 26.
Artículo en Inglés | MEDLINE | ID: mdl-38266091

RESUMEN

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.

4.
Sci Rep ; 13(1): 17006, 2023 Oct 09.
Artículo en Inglés | MEDLINE | ID: mdl-37813929

RESUMEN

The sealing characteristics of the geological formation located above a CO2 storage reservoir, the so-called caprock, are essential to ensure efficient geological carbon storage. If CO2 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 CO2-enriched fluid was continuously injected in a faulted caprock analogue. Our results show that the CO2 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 CO2-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 CO2 in fault zones.

5.
Environ Sci Technol ; 57(36): 13487-13495, 2023 09 12.
Artículo en Inglés | MEDLINE | ID: mdl-37643154

RESUMEN

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, O2, CO2, and CH4 concentrations. The results revealed that groundwater contributed ∼60% of CO2 and ∼30% of CH4 inputs to the stream, supporting stream CO2 and CH4 emissions to the atmosphere. Furthermore, diurnal variations in stream metabolism (-0.6 to 0.6 mol O2 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.


Asunto(s)
Dióxido de Carbono , Agua Subterránea , Ríos , Factores de Tiempo , Atmósfera , Carbono , Gases
6.
Water Res ; 235: 119880, 2023 May 15.
Artículo en Inglés | MEDLINE | ID: mdl-36958224

RESUMEN

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 (222Rn) has been used for decades as a natural indicator of surface water infiltration, as it can provide quantitative information on GRT. However, models using 222Rn as a tracer of GRT are often based on a set of highly simplifying assumptions, including spatially homogenous 222Rn production and exclusively advective mass transport within the aquifer. In this paper, we use the integrated surface-subsurface hydrological model HydroGeoSphere (HGS) to simulate 222Rn transport, production, and decay in a bank filtration context. Spatially variable 222Rn production, based on experimental data, is explicitly considered. We show that variable 222Rn production rates, coupled with hydrodispersive mixing of groundwater, may lead to large biases in GRT estimates. Under certain transient conditions however, changes in tracer-derived GRTs correlate well with changes in mean groundwater age. Whereas 222Rn-derived GRTs may only be reliable under a narrow range of field conditions, 222Rn may serve as a powerful tracer of changes in mean GRT even in complex and heterogenous environments.


Asunto(s)
Agua Subterránea , Reproducibilidad de los Resultados , Recursos Hídricos , Ríos , Agua
7.
Sci Total Environ ; 860: 160407, 2023 Feb 20.
Artículo en Inglés | MEDLINE | ID: mdl-36427729

RESUMEN

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. Here we correlate the distribution of arsenic contaminated wells with the fluvial dynamics in the Amazon basin. Groundwater was sampled from tube wells along the Amazon River and its main tributaries in three distinct regions in Peru and Brazil. For each sample, the major and trace element concentrations were analyzed, and the position of the well within the sedimentary structure was determined. The results show that aquifers in poorly weathered sediments deposited by sediment-rich rivers are prone to mobilization and accumulation of aqueous arsenic and manganese, both in sub-Andean foreland basins, and in floodplains downstream. Two zones at risk are distinguished: aquifers in the channel-dominated part of the floodplain (CDF) and aquifers in the overbank deposits on the less-dynamic part of the floodplain (LDF). Some 70 % of the wells located on the CDF and 20 % on the LDF tap groundwater at concentrations exceeding the WHO guideline of 10 µg/L arsenic (max. 430 µg/L), and 70 % (CDF) and 50 % (LDF) exceeded 0.4 mg/L manganese (max. 6.6 mg/L). None of the water samples located outside the actual floodplain of sediment-rich rivers, or on riverbanks of sediment-poor rivers exceed 5 µg/L As, and only 4 % exceeded 0.4 mg/L Mn. The areas of highest risk can be delineated using satellite imagery. We observe similar patterns as in affected river basins in South and Southeast Asia indicating a key role of sedimentation processes and fluvial geomorphology in priming arsenic and manganese contamination in aquifers.


Asunto(s)
Arsénico , Agua Subterránea , Contaminantes Químicos del Agua , Humanos , Manganeso/análisis , Arsénico/análisis , Brasil , Contaminantes Químicos del Agua/análisis , Agua Subterránea/química , Monitoreo del Ambiente
8.
Water Res ; 214: 118199, 2022 May 01.
Artículo en Inglés | MEDLINE | ID: mdl-35220067

RESUMEN

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 (CH4) 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 N2) alongside highly increasing CH4, implying that a free gas phase comprised mainly of CH4 is formed within the aquifer. In contrast, Helium (He) concentrations are high within the CH4 (gas) producing zone, suggesting longer (groundwater) residence times. We hypothesized that the observed free (CH4) 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 (CH4) 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 CH4, 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.

9.
Water Res ; 200: 117300, 2021 Jul 15.
Artículo en Inglés | MEDLINE | ID: mdl-34107428

RESUMEN

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. Carbon isotope signatures (δ13C-CH4, δ13C-DOC, δ13C-DIC) provided evidence that fermentation, methanogenesis and methanotrophy are actively contributing to the As heterogeneity. Methanogenesis occurred concurrently where As levels are high (>200 µg/L) and DOC-enriched aquitard pore water infiltrates into the aquifer. Along the flowpath to the Holocene/Pleistocene aquifer transition, methane oxidation causes a strong shift in δ13C-CH4 from -87‰ to +47‰, indicating high reactivity. These findings demonstrate a previously overlooked role of methane cycling and DOC infiltration in high-As aquifers.


Asunto(s)
Arsénico , Agua Subterránea , Contaminantes Químicos del Agua , Arsénico/análisis , Carbono , Monitoreo del Ambiente , Humanos , Metano , Contaminantes Químicos del Agua/análisis
10.
Nature ; 593(7858): 228-232, 2021 05.
Artículo en Inglés | MEDLINE | ID: mdl-33981051

RESUMEN

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 sensitivity1,2. Reliable LGM temperatures come from high-latitude ice cores3,4, but substantial disagreement exists between proxy records in the low latitudes1,5-8, 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 water9,10. Dissolved noble gases are suitable tracers of LGM temperature because of their complete insensitivity to biological and chemical processes and the ubiquity of LGM-aged groundwater around the globe11,12. However, although several individual noble gas studies have found substantial tropical LGM cooling13-16, they have used different methodologies and provide limited spatial coverage. Here we use noble gases in groundwater to show that the low-altitude, low-to-mid-latitude land surface (45 degrees south to 35 degrees north) cooled by 5.8 ± 0.6 degrees Celsius (mean ± 95% confidence interval) during the LGM. Our analysis includes four decades of groundwater noble gas data from six continents, along with new records from the tropics, all of which were interpreted using the same physical framework. Our land-based result broadly supports a recent reconstruction based on marine proxy data assimilation1 that suggested greater climate sensitivity than previous estimates5-7.


Asunto(s)
Cambio Climático/historia , Clima , Frío , Cubierta de Hielo , Altitud , Agua Subterránea/química , Historia Antigua , Gases Nobles/análisis , Reproducibilidad de los Resultados , Solubilidad
11.
J Contam Hydrol ; 238: 103773, 2021 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-33540239

RESUMEN

Urban groundwater management requires a thorough and robust scientific understanding of flow and transport processes. 3H/3He 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 3H/3He apparent groundwater ages and 4He 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 3H/3He lab-based ages and predicted ages from the 3H/3He-4He 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 (18O and 2H), 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.


Asunto(s)
Agua Subterránea , Tetracloroetileno , Monitoreo del Ambiente , Helio/análisis , Isótopos/análisis
12.
MethodsX ; 7: 101038, 2020.
Artículo en Inglés | MEDLINE | ID: mdl-32963969

RESUMEN

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, N2, O2, CO2) 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 CH4, O2 and N2 at m / z = 15 and 16; or Ne, Ar and H2O 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.

13.
Sci Rep ; 10(1): 6949, 2020 Apr 24.
Artículo en Inglés | MEDLINE | ID: mdl-32332786

RESUMEN

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.

14.
Sci Total Environ ; 717: 137143, 2020 May 15.
Artículo en Inglés | MEDLINE | ID: mdl-32062264

RESUMEN

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. Here we report a detailed characterisation of the Van Phuc aquifer in the Red River Delta region, Vietnam, where high-As groundwater from a Holocene aquifer is being drawn into a low-As Pleistocene aquifer. This study includes data from eight years (2010-2017) of groundwater observations to develop an understanding of the spatial and temporal evolution of the redox status and groundwater hydrochemistry. Arsenic concentrations were highly variable (0.5-510 µg/L) over spatial scales of <200 m. Five hydro(geo)chemical zones (indicated as A to E) were identified in the aquifer, each associated with specific As mobilisation and retardation processes. At the riverbank (zone A), As is mobilised from freshly deposited sediments where Fe(III)-reducing conditions occur. Arsenic is then transported across the Holocene aquifer (zone B), where the vertical intrusion of evaporative water, likely enriched in dissolved organic matter, promotes methanogenic conditions and further release of As (zone C). In the redox transition zone at the boundary of the two aquifers (zone D), groundwater arsenic concentrations decrease by sorption and incorporations onto Fe(II) carbonates and Fe(II)/Fe(III) (oxyhydr)oxides under reducing conditions. The sorption/incorporation of As onto Fe(III) minerals at the redox transition and in the Mn(IV)-reducing Pleistocene aquifer (zone E) has consistently kept As concentrations below 10 µg/L for the studied period of 2010-2017, and the location of the redox transition zone does not appear to have propagated significantly. Yet, the largest temporal hydrochemical changes were found in the Pleistocene aquifer caused by groundwater advection from the Holocene aquifer. This is critical and calls for detailed investigations.

15.
Environ Sci Technol ; 54(3): 1562-1572, 2020 02 04.
Artículo en Inglés | MEDLINE | ID: mdl-31904942

RESUMEN

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 N2 to argon (Ar) to quantify net production of N2 via denitrification by separating the biologically generated N2 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 N2 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 (N2, He, Ar, and Kr) combined with a physically meaningful excess air model, we quantified N2 originating from denitrification. Consequently, we were able to study the spatiotemporal dynamics of N2 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.


Asunto(s)
Desnitrificación , Agua Subterránea , Espectrometría de Masas , Nitrógeno , Gases Nobles
16.
Sci Total Environ ; 660: 1219-1231, 2019 Apr 10.
Artículo en Inglés | MEDLINE | ID: mdl-30743917

RESUMEN

This study presents a novel data set of noble gas compositions and 3H/3He 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. 3H/3He 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.

17.
Environ Sci Technol ; 53(3): 1463-1470, 2019 02 05.
Artículo en Inglés | MEDLINE | ID: mdl-30576112

RESUMEN

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 ( ki). 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 N2), 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.


Asunto(s)
Gases , Gases Nobles , Espectrometría de Masas , Solubilidad , Temperatura
18.
Sci Rep ; 7(1): 313, 2017 03 22.
Artículo en Inglés | MEDLINE | ID: mdl-28331216

RESUMEN

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.

19.
Environ Sci Process Impacts ; 19(3): 405-413, 2017 Mar 22.
Artículo en Inglés | MEDLINE | ID: mdl-28186521

RESUMEN

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.


Asunto(s)
Simulación de Dinámica Molecular , Gases Nobles/química , Agua/química , Fraccionamiento Químico , Difusión , Isótopos/química , Modelos Químicos
20.
Environ Sci Technol ; 50(24): 13455-13463, 2016 12 20.
Artículo en Inglés | MEDLINE | ID: mdl-27993051

RESUMEN

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.


Asunto(s)
Gases , Espectrometría de Masas , Lagos , Suelo , Agua
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