Contribution of the diffusive exchange method to the characterization of pore-water in consolidated argillaceous rocks

Savoye, S.; Michelot, Jean‐Luc; Wittebroodt, Charles; Altinier, M.V.

doi:10.1016/j.jconhyd.2006.02.010

Cited by 44 publications

(20 citation statements)

References 26 publications

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“…In general, physical extraction methods are laborious and have the potential for evaporative isotopic fractionation caused by storage, multistep procedures, or by incomplete recovery of the water or evaporative loss during handling. Alternative methods for obtaining pore water isotopes from cores include radial diffusion mass-balance mixing cells (Altinier et al, 2007;Bensenouci et al, 2013;Rubel et al, 2002;Savoye et al, 2006;van der Kamp et al, 1996) or direct equilibration of the pore water in core sub-samples using helium-CO 2 or a He-H 2 catalyst mixtures with headspace gas-water equilibration (Hendry et al, 2004;Kelln et al, 2007;Koehler et al, 2000). Wassenaar et al (2008) proposed a novel method for measuring the δ 2 H and δ 18 O of pore water in saturated and unsaturated geologic (core, soil) samples by using a direct vapour equilibration and laser spectrometry (DVE-LS) approach.…”

Section: Published By Copernicus Publications On Behalf Of the Europementioning

confidence: 99%

Determining the stable isotope composition of pore water from saturated and unsaturated zone core: improvements to the direct vapour equilibration laser spectrometry method

Hendry

Schmeling

Wassenaar

et al. 2015

Hydrol. Earth Syst. Sci.

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Abstract.A method to measure the δ 2 H and δ 18 O composition of pore waters in saturated and unsaturated geologic core samples using direct vapour equilibration and laser spectrometry (DVE-LS) was first described in 2008, and has since been rapidly adopted. Here, we describe a number of important methodological improvements and limitations encountered in routine application of DVE-LS over several years. Generally, good comparative agreement, as well as accuracy, is obtained between core pore water isotopic data obtained using DVE-LS and that measured on water squeezed from the same core. In complex hydrogeologic settings, high-resolution DVE-LS depth profiles provide greater spatial resolution of isotopic profiles compared to long-screened or nested piezometers. When fluid is used during drilling and coring (e.g. water rotary or wet sonic drill methods), spiking the drill fluid with 2 H can be conducted to identify core contamination. DVE-LS analyses yield accurate formational isotopic data for fine-textured core (e.g. clay, shale) samples, but are less effective for cores obtained from saturated permeable (e.g. sand, gravels) geologic media or on chip samples that are easily contaminated by wet rotary drilling fluid. Data obtained from DVE-LS analyses of core samples collected using wet (contamination by drill water) and dry sonic (water loss by heating) methods were also problematic. Accurate DVE-LS results can be obtained on core samples with gravimetric water contents > 5 % by increasing the sample size tested. Inexpensive Ziploc ™ gassampling bags were determined to be as good as, if not better than, other, more expensive specialty bags. Sample storage in sample bags provides acceptable results for up to 10 days of storage; however, measurable water loss, as well as evaporitic isotopic enrichment, occurs for samples stored for up to 6 months. With appropriate care taken during sample collection and storage, the DVE-LS approach for obtaining high-resolution pore water isotopic data is a promising alternative to study the hydrogeology of saturated and unsaturated sediments. Eliminating analytical interferences from volatile organics remains a challenge.

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Section: Published By Copernicus Publications On Behalf Of the Europementioning

confidence: 99%

Determining the stable isotope composition of pore water from saturated and unsaturated zone core: improvements to the direct vapour equilibration laser spectrometry method

Hendry

Schmeling

Wassenaar

et al. 2015

Hydrol. Earth Syst. Sci.

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“…Sampling water from wells is not possible in formations with very low permeabilities or at larger depths, and pore water data have to be obtained by indirect methods from core samples [ Kelln et al , 2001; Sacchi et al , 2001; Pearson et al , 2003; Savoye et al , 2006]. While Remenda et al [1994] partly applied squeezing, Hendry and Wassenaar [1999] (for part of the data) and Patriarche et al [2004b] (for Cl − ) used radial diffusion cells with equilibration via a water phase.…”

Section: Introductionmentioning

confidence: 99%

Stable water isotopes in pore water of Jurassic argillaceous rocks as tracers for solute transport over large spatial and temporal scales

Gimmi

Waber

Gautschi

et al. 2007

Water Resources Research

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[1] In order to characterize the large-scale transport properties of the Opalinus Clay formation, the pore water isotope composition (d 18 O and d 2 H) was determined on samples from the deep borehole Benken (northeastern Switzerland) across Jurassic argillaceous rocks. The sequence of claystones and marls, delimited by two aquifers, is located at depth from about 400 to 700 m and exhibits very low hydraulic conductivities (below 10 À13 m s À1). The isotope data of the pore water were obtained from core samples by diffusive vapor equilibration, vacuum distillation, and squeezing. Compared with the other methods, vacuum distillation led to too low values. To evaluate the large-scale transport properties of the formation, we performed a series of advective-dispersive model calculations and compared them with the experimental data. In accordance with the hydrogeological history, we varied initial and boundary conditions as well as model parameters. The main results can be summarized as follows: (1) Molecular diffusion to the underlying aquifer can explain the general features of the isotope profiles, (2) no signatures of advective flow could be detected, (3) the evolution time is of the order of 0.5-1 Ma (relying on laboratory diffusion coefficients) with a possible range of about 0.2-2 Ma, which is geologically plausible, and (4) parameters measured on small scales (centimeters or meters and months) are also plausible at the formation scale (tens of meters and millions of years) for the sediments investigated.Citation: Gimmi, T., H. N. Waber, A. Gautschi, and A. Rübel (2007), Stable water isotopes in pore water of Jurassic argillaceous rocks as tracers for solute transport over large spatial and temporal scales, Water Resour. Res., 43, W04410,

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“…The volumetric moisture content, , is calculated from the water content using the following expression [27]:…”

Section: Petrophysical Measurementsmentioning

confidence: 99%

Effect of Water Saturation on the Diffusion/Adsorption of ²²Na and Cesium onto the Callovo-Oxfordian Claystones

et al. 2017

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The diffusion and adsorption behaviors of sodium and cesium were investigated in the Callovo-Oxfordian claystones (France) under unsaturated conditions. Through-, out-, and in-diffusion laboratory experiments were performed on intact and compacted samples. These samples were partially saturated using an osmotic method for imposed suction up to 9 MPa. This specific technique enabled us to obtain water saturation degree ranging from 81% to 100% for intact samples and from 70% to 100% for compacted materials. The results showed a very low impact of water saturation on the extent of adsorption for 22 Na and cesium, onto intact and compacted materials. Such observations suggest that the saturation degrees were not low enough to limit the access of cations to adsorption sites on clay surfaces. At full saturation, enhanced diffusion for 22 Na and cesium was clearly evidenced onto intact and compacted samples. Under unsaturated conditions, the diffusion behavior for Cs and 22 Na was not only slower but also distinct as compared to fully saturated samples. For the intact rock and under suction of 1.9 MPa, the Cs diffusivity was reduced by a factor of 17, whereas for sodium, it was reduced by a factor of 5. Explanation was then proposed to explain such a difference.

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Contribution of the diffusive exchange method to the characterization of pore-water in consolidated argillaceous rocks

Cited by 44 publications

References 26 publications

Determining the stable isotope composition of pore water from saturated and unsaturated zone core: improvements to the direct vapour equilibration laser spectrometry method

Determining the stable isotope composition of pore water from saturated and unsaturated zone core: improvements to the direct vapour equilibration laser spectrometry method

Stable water isotopes in pore water of Jurassic argillaceous rocks as tracers for solute transport over large spatial and temporal scales

Effect of Water Saturation on the Diffusion/Adsorption of ²²Na and Cesium onto the Callovo-Oxfordian Claystones

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Contribution of the diffusive exchange method to the characterization of pore-water in consolidated argillaceous rocks

Cited by 44 publications

References 26 publications

Determining the stable isotope composition of pore water from saturated and unsaturated zone core: improvements to the direct vapour equilibration laser spectrometry method

Determining the stable isotope composition of pore water from saturated and unsaturated zone core: improvements to the direct vapour equilibration laser spectrometry method

Stable water isotopes in pore water of Jurassic argillaceous rocks as tracers for solute transport over large spatial and temporal scales

Effect of Water Saturation on the Diffusion/Adsorption of 22Na and Cesium onto the Callovo-Oxfordian Claystones

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Effect of Water Saturation on the Diffusion/Adsorption of ²²Na and Cesium onto the Callovo-Oxfordian Claystones