Anisotropic diffusion at the field scale in a 4-year multi-tracer diffusion and retention experiment – I: Insights from the experimental data

Abstract Claystones are considered worldwide as barrier materials for nuclear waste repositories. In the Mont Terri underground research laboratory (URL), a nearly 4-year diffusion and retention (DR) experiment has been performed in Opalinus Clay. It aimed at (1) obtaining data at larger space and time scales than in laboratory experiments and (2) under relevant in situ conditions with respect to pore water chemistry and mechanical stress, (3) quantifying the anisotropy of in situ diffusion, and (4) exploring possible effects of a borehole-disturbed zone. The experiment included two tracer injection intervals in a borehole perpendicular to bedding, through which traced artificial pore water (APW) was circulated, and a pressure monitoring interval. The APW was spiked with neutral tracers (HTO, HDO, H2O-18), anions (Br, I, SeO4), and cations (Na-22, Ba-133, Sr-85, Cs-137, Co-60, Eu-152, stable Cs, and stable Eu). Most tracers were added at the beginning, some were added at a later stage. The hydraulic pressure in the injection intervals was adjusted according to the measured value in the pressure monitoring interval to ensure transport by diffusion only. Concentration time-series in the APW within the borehole intervals were obtained, as well as 2D concentration distributions in the rock at the end of the experiment after overcoring and subsampling which resulted in �250 samples and �1300 analyses. As expected, HTO diffused the furthest into the rock, followed by the anions (Br, I, SeO4) and by the cationic sorbing tracers (Na-22, Ba-133, Cs, Cs-137, Co-60, Eu-152). The diffusion of SeO4 was slower than that of Br or I, approximately proportional to the ratio of their diffusion coefficients in water. Ba-133 diffused only into �0.1 m during the �4 a. Stable Cs, added at a higher concentration than Cs-137, diffused further into the rock than Cs-137, consistent with a non-linear sorption behavior. The rock properties (e.g., water contents) were rather homogeneous at the centimeter scale, with no evidence of a borehole-disturbed zone. In situ anisotropy ratios for diffusion, derived for the first time directly from field data, are larger for HTO and Na-22 (�5) than for anions (�3�4 for Br and I). The lower ionic strength of the pore water at this location (�0.22 M) as compared to locations of earlier experiments in the Mont Terri URL (�0.39 M) had no notable effect on the anion accessible pore fraction for Cl, Br, and I: the value of 0.55 is within the range of earlier data. Detailed transport simulations involving different codes will be presented in a companion paper.

Identifiability of diffusion and sorption parameters from in situ diffusion experiments by using simultaneously tracer dilution and claystone data

In situ diffusion experiments are performed in geological formations at underground research laboratories to overcome the limitations of laboratory diffusion experiments and investigate scale effects. Tracer concentrations are monitored at the injection interval during the experiment (dilution data) and measured from host rock samples around the injection interval at the end of the experiment (overcoring data). Diffusion and sorption parameters are derived from the inverse numerical modeling of the measured tracer data. The identifiability and the uncertainties of tritium and Na-22(+) diffusion and sorption parameters are studied here by synthetic experiments having the same characteristics as the in situ diffusion and retention (DR) experiment performed on Opalinus Clay. Contrary to previous identifiability analyses of in situ diffusion experiments, which used either dilution or overcoring data at approximate locations, our analysis of the parameter identifiability relies simultaneously on dilution and overcoring data, accounts for the actual position of the overcoring samples in the claystone, uses realistic values of the standard deviation of the measurement errors, relies on model identification criteria to select the most appropriate hypothesis about the existence of a borehole disturbed zone and addresses the effect of errors in the location of the sampling profiles. The simultaneous use of dilution and overcoring data provides accurate parameter estimates in the presence of measurement errors, allows the identification of the right hypothesis about the borehole disturbed zone and diminishes other model uncertainties such as those caused by errors in the volume of the circulation system and the effective diffusion coefficient of the filter. The proper interpretation of the experiment requires the right hypothesis about the borehole disturbed zone. A wrong assumption leads to large estimation errors. The use of model identification criteria helps in the selection of the best model. Small errors in the depth of the overcoring samples lead to large parameter estimation errors. Therefore, attention should be paid to minimize the errors in positioning the depth of the samples. The results of the identifiability analysis do not depend on the particular realization of random numbers. (C) 2012 Elsevier B.V. All rights reserved.

Transport of 234U in the Opalinus Clay on centimetre to decimetre scales

The Opalinus Clay formation in North Switzerland is a potential host rock for a deep underground radioactive waste repository. The distribution of U-238, U-234 and Th-230 was studied in rock samples of the Opalinus Clay from an exploratory borehole at Benken (Canton of Zurich) using MC-ICP-MS. The aim of U-234 was to assess the in situ, long-term migration behaviour in this rock. Very low hydraulic conductivities of the Opalinus Clay, reducing potential of the pore water and its chemical equilibrium with the host rock are expected to render both U-238 and Th-230 immobile. If U is heterogeneously distributed in the Opalinus Clay, gradients in the supply of U-234 from the rock matrix to the pore water by the decay of U-238 will be established. Diffusive redistribution separates U-234 from its immobile parent U-238 resulting in bulk rock U-234/U-238 activity disequilibria. These may provide a means of estimating the mobility of U-234 in the rock if the diffusion rate of U-234 is significant compared to its decay rate. Sampling was carried out on two scales. Drilling of cm-spaced samples from the drill-core was done to study mobility over short distances and elucidate possible small-scale lithological control. Homogenized 25-cm-long portions of a 2-m-long drill-core section were prepared to provide information on transport over a longer distance. Variations in U and/or Th content on the cm-scale between clays and carbonate-sandy layers are revealed by beta-scanning, which shows that the (dominant) clay is richer in both elements. Samples were digested using aqua regia followed by total HF dissolution, yielding two fractions. in all studied samples U was found to be concentrated in the HF digestion fraction. It has a high U/Th ratio and a study by SEM-EDS points to sub-mu m up to several mu m in size zircon grains as the main U-rich phase. This fraction consistently has U-234/U-238 activity ratios below unity. The minute zircon grains constitute the major reservoir of U in the rock and act as constant rate suppliers of U-234 into the rock matrix and the pore water. The aqua regia leach fraction was found to be enriched in Th, and complementary to the HF fraction, having U-234/U-238 activity ratios above unity. It is believed that these U activity ratios reflect the surplus of having U-234 delivered from the zircon grains. Some cm-spaced samples show bulk rock U-234/U-238 activity ratios that are markedly out of equilibrium. In most of them a striking negative correlation between the total U content and the bulk rock U-234/U-238 activity ratios is observed. This is interpreted to indicate net U-234 transfer from regions of higher supply of U-234 towards those of lower supply which is, in most cases, equivalent to transfer from clayey towards carbonate/sandy portions of the rock. In contrast, the 25 cm averaged samples all have uniform bulk rock U-234/U-238 activity ratios in equilibrium, indicating U immobility in the last 1-1.5 Ma on this spatial scale. It is concluded that the small-scale lithological variations which govern U spatial distribution in the Opalinus Clay are the major factor determining U-234 in situ supply rates, regulating its diffusive fluxes and controlling the observed bulk rock U-234/U-238 activity ratios. A simple box-model is presented to simulate the measured bulk rock U-234/U-238 activity ratios and to give an additional insight into the studied system. (C) 2008 Elsevier Ltd. All rights reserved.

Diffusion of HTO, Br-, I-, Cs+, Sr-85(2+) and Co-60(2+) in a clay formation: Results and modelling from an in situ experiment in Opalinus Clay

The migration of radioactive and chemical contaminants in clay materials and argillaceous host rocks is characterised by diffusion and retention processes. Valuable information on such processes can be gained by combining diffusion studies at laboratory scale with field migration tests. In this work, the outcome of a multi-tracer in situ migration test performed in the Opalinus Clay formation in the Mont Terri underground rock laboratory (Switzerland) is presented. Thus, 1.16 x 10(5) Bq/L of HTO, 3.96 x 10(3) Bq/L of Sr-85, 6.29 x 10(2) Bq/L of Co-60, 2.01 x 10(-3) mol/L Cs, 9.10 x 10(-4) mol/L I and 1.04 x 10(-3) mol/L Br were injected into the borehole. The decrease of the radioisotope concentrations in the borehole was monitored using in situ gamma-spectrometry. The other tracers were analyzed with state-of-the-art laboratory procedures after sampling of small water aliquots from the reservoir. The diffusion experiment was carried out over a period of one year after which the interval section was overcored and analyzed. Based on the experimental data from the tracer evolution in the borehole and the tracer profiles in the rock, the diffusion of tracers was modelled with the numerical code CRUNCH. The results obtained for HTO (H-3), I- and Br- confirm previous lab and in situ diffusion data. Anionic fluxes into the formation were smaller compared to HTO because of anion exclusion effects. The migration of the cations Sr-85(2+), Cs+ and Co-60(2+) was found to be governed by both diffusion and sorption processes. For Sr-85(2+), the slightly higher diffusivity relative to HTO and the low sorption value are consistent with laboratory diffusion measurements on small-scale samples. In the case of Cs+, the numerically deduced high diffusivity and the Freundlich-type sorption behaviour is also supported by ongoing laboratory data. For Co, no laboratory diffusion data were yet available for comparison; however, the modelled data suggests that Co-60(2+) sorption was weaker than would be expected from available batch sorption data. Overall, the results demonstrate the feasibility of the experimental setup for obtaining high-quality diffusion data for conservative and sorbing tracers. (C) 2007 Elsevier Ltd. All rights reserved.

Addendum: search for ν μ → ν e oscillations with the OPERA experiment in the CNGS beam

A first result of the search for ν ( )μ( ) → ν ( )e( ) oscillations in the OPERA experiment, located at the Gran Sasso Underground Laboratory, is presented. The experiment looked for the appearance of ν ( )e( ) in the CNGS neutrino beam using the data collected in 2008 and 2009. Data are compatible with the non-oscillation hypothesis in the three-flavour mixing model. A further analysis of the same data constrains the non-standard oscillation parameters θ (new) and suggested by the LSND and MiniBooNE experiments. For large values (>0.1 eV(2)), the OPERA 90% C.L. upper limit on sin(2)(2θ (new)) based on a Bayesian statistical method reaches the value 7.2 × 10(−3).

New results on ν μ → ν τ appearance with the OPERA experiment in the CNGS beam

The OPERA neutrino experiment is designed to perform the first observation of neutrino oscillations in direct appearance mode in the νμ→ντ channel, via the detection of the τ-leptons created in charged current ντ interactions. The detector, located in the underground Gran Sasso Laboratory, consists of an emulsion/lead target with an average mass of about 1.2 kt, complemented by electronic detectors. It is exposed to the CERN Neutrinos to Gran Sasso beam, with a baseline of 730 km and a mean energy of 17 GeV. The observation of the first ντ candidate event and the analysis of the 2008-2009 neutrino sample have been reported in previous publications. This work describes substantial improvements in the analysis and in the evaluation of the detection efficiencies and backgrounds using new simulation tools. The analysis is extended to a sub-sample of 2010 and 2011 data, resulting from an electronic detector-based pre-selection, in which an additional ντ candidate has been observed. The significance of the two events in terms of a νμ→ντ oscillation signal is of 2.40 σ.

Measurement of the neutrino velocity with the OPERA detector in the CNGS beam using the 2012 dedicated data

In spring 2012 CERN provided two weeks of a short bunch proton beam dedicated to the neutrino velocity measurement over a distance of 730 km. The OPERA neutrino experiment at the underground Gran Sasso Laboratory used an upgraded setup compared to the 2011 measurements, improving the measurement time accuracy. An independent timing system based on the Resistive Plate Chambers was exploited providing a time accuracy of ∼1 ns. Neutrino and anti-neutrino contributions were separated using the information provided by the OPERA magnetic spectrometers. The new analysis profited from the precision geodesy measurements of the neutrino baseline and of the CNGS/LNGS clock synchronization. The neutrino arrival time with respect to the one computed assuming the speed of light in vacuum is found to be δtν≡TOFc−TOFν=(0.6±0.4 (stat.)±3.0 (syst.)) ns and δtν¯≡TOFc−TOFν¯=(1.7±1.4 (stat.)±3.1 (syst.)) ns for νμ and ν¯μ, respectively. This corresponds to a limit on the muon neutrino velocity with respect to the speed of light of −1.8×10−6<(vν−c)/c<2.3×10−6 at 90% C.L. This new measurement confirms with higher accuracy the revised OPERA result.

Search for νμ→νe oscillations with the OPERA experiment in the CNGS beam

A first result of the search for nu(mu)->nu(e) oscillations in the OPERA experiment, located at the Gran Sasso Underground Laboratory, is presented. The experiment looked for the appearance of nu(e) in the CNGS neutrino beam using the data collected in 2008 and 2009. Data are compatible with the non-oscillation hypothesis in the three-flavour mixing model. A further analysis of the same data constrains the non-standard oscillation parameters theta(new) and Delta m(new)(2) suggested by the LSND and MiniBooNE experiments. For large Delta m(new)(2) values (>0.1 eV(2)), the OPERA 90% C.L. upper limit on sin(2)(2 theta(new)) based on a Bayesian statistical method reaches the value 7.2 x 10(-3).

The neutron background of the XENON100 dark matter experiment

TheXENON100 experiment, installed underground at the LaboratoriNazionali del Gran Sasso, aims to directly detect dark matter in the form of weakly interacting massive particles (WIMPs) via their elastic scattering off xenon nuclei. This paper presents a study on the nuclear recoil background of the experiment, taking into account neutron backgrounds from (alpha, n) reactions and spontaneous fission due to natural radioactivity in the detector and shield materials, as well as muon-induced neutrons. Based on MonteCarlo simulations and using measured radioactive contaminations of all detector components, we predict the nuclear recoil backgrounds for the WIMP search results published by theXENON100 experiment in 2011 and 2012, 0.11(-0.04)(+0.08) events and 0.17(-0.07)(+0.12) events, respectively, and conclude that they do not limit the sensitivity of the experiment.

Response of the XENON100 Dark Matter Detector to Nuclear Recoils

Results from the nuclear recoil calibration of the XENON100 dark matter detector installed underground at the Laboratori Nazionali del Gran Sasso, Italy are presented. Data from measurements with an external AmB(241)e neutron source are compared with a detailed Monte Carlo simulation which is used to extract the energy-dependent charge-yield Q(y) and relative scintillation efficiency L-eff. A very good level of absolute spectral matching is achieved in both observable signal channels-scintillation S1 and ionization S2-along with agreement in the two-dimensional particle discrimination space. The results confirm the validity of the derived signal acceptance in earlier reported dark matter searches of the XENON100 experiment.

Natural Tracers in recent groundwaters from different Alpine aquifers

Groundwater with underground residence times between days and a few years have been investigated over more than 20 years from 487 remote sites located in different aquifer types in the Alpine belt. Analysis of the data reveals that groundwaters evolved in crystalline, evaporite, carbonate, molasse, and flysch aquifers can be clearly distinguished based on their major and trace element composition and degree of mineralisation. A further subdivision can be made even within one aquifer type based on the trace element compositions, which are characteristic for the lithologic environment. Major and trace element concentrations can be quantitatively described by interaction of the groundwater with the aquifer- specific mineralogy along the flow path. Because all investigated sites show minimal anthropogenic influences, the observed concentration ranges represent the natural background concentrations and can thus serve as a “geo-reference” for recent groundwaters from these five aquifer types. This “geo-reference” is particularly useful for the identification of groundwater contamination. It further shows that drinking water standards can be grossly exceeded for critical elements by purely natural processes

Measurement of the TeV atmospheric muon charge ratio with the complete OPERA data set

The OPERA detector, designed to search for νμ → ντ oscillations in the CNGS beam, is located in the underground Gran Sasso laboratory, a privileged location to study TeV-scale cosmic rays. For the analysis here presented, the detector was used to measure the atmospheric muon charge ratio in the TeV region. OPERA collected chargeseparated cosmic ray data between 2008 and 2012. More than 3 million atmospheric muon events were detected and reconstructed, among which about 110000 multiple muon bundles. The charge ratio Rμ ≡ Nμ+/Nμ− was measured separately for single and for multiple muon events. The analysis exploited the inversion of the magnet polarity which was performed on purpose during the 2012 Run. The combination of the two data sets with opposite magnet polarities allowedminimizing systematic uncertainties and reaching an accurate determination of the muon charge ratio. Data were fitted to obtain relevant parameters on the composition of primary cosmic rays and the associated kaon production in the forward fragmentation region. In the surface energy range 1–20 TeV investigated by OPERA, Rμ is well described by a parametric model including only pion and kaon contributions to themuon flux, showing no significant contribution of the prompt component. The energy independence supports the validity of Feynman scaling in the fragmentation region up to 200 TeV/nucleon primary energy.

The open cut: Mining, transnational corporations and local populations

The rapid expansion of the mineral and metal mining sector in the past decade was accompanied by an increase in social conflicts. What are the impacts of large-scale mining operations? What are the strategies used by transnational corporations to gain access to underground resources and legitimize their activities? And how do local and indigenous communities confronted with mining react to, negotiate with and resist these activities? This book covers 13 case studies of copper, gold, uranium and other mining operations, situated in Latin America, Africa, Asia, Australia and Switzerland. With an extensive introduction to the subject and a systematic comparison across mining operations in different phases of development and social contexts, it serves as a primer and reference book for activists, students and researchers alike.

A Forgotten Original or an Original Copy? On MS. Douce 387 in the Bodleian Library: Collecting Early Modern Festival Books

Focusing on one manuscript, today in the Bodleian Library, Oxford, this chapter deals with the question how early modern objects became collectable items. The manuscript is categorized as MS. Douce 387 and its name indicates that it came from the collection of Francis Douce (1757–1834), who was keeper of manuscripts in the British Museum from 1799 until 1811. MS. Douce 387 is described in the catalogue of the Douce’ian collection as the “presentation copy with coloured designs by Marten de Vos and others” of the 1595 printed festival book Descriptio publicae gratulationis … in adventu … Ernesti archiducis Austriae. This festival book, printed in Antwerp’s Plantin-Moretus press, was commissioned by the magistrate of the city of Antwerp to commemorate the Joyous Entry of Archduke Ernest of Austria from June 1594; that an “archducal copy” bound in red velvet was commissioned as well and was owned by the Archduke is know as well. However, first research showed that Oxford copy cannot be this “archducal copy” or Marten de Vos’s artist’s copy even though it is the only know version with a handwritten text and hand-drawn illustrations. It rather should be examined as something totally different altogether. The main question remains why someone then commissioned a hand made version of this festival book, something unknown for other books of this genre? Why would someone between 1600 and 1800 sit down and copy texts and prints from a collectable book? Why was there such an on-going interest in early modern festival books? Could this manuscript be the only later made copy of the “archducal volume” or is it rather a forgery made for the European collectors’ market?

Dissolution-Precipitation in Porous Media: Experiments and Modelling

The evolution of porosity due to dissolution/precipitation processes of minerals and the associated change of transport parameters are of major interest for natural geological environments and engineered underground structures. We designed a reproducible and fast to conduct 2D experiment, which is flexible enough to investigate several process couplings implemented in the numerical code OpenGeosys-GEM (OGS-GEM). We investigated advective-diffusive transport of solutes, effect of liquid phase density on advective transport, and kinetically controlled dissolution/precipitation reactions causing porosity changes. In addition, the system allowed to investigate the influence of microscopic (pore scale) processes on macroscopic (continuum scale) transport. A Plexiglas tank of dimension 10 × 10 cm was filled with a 1 cm thick reactive layer consisting of a bimodal grain size distribution of celestite (SrSO4) crystals, sandwiched between two layers of sand. A barium chloride solution was injected into the tank causing an asymmetric flow field to develop. As the barium chloride reached the celestite region, dissolution of celestite was initiated and barite precipitated. Due to the higher molar volume of barite, its precipitation caused a porosity decrease and thus also a decrease in the permeability of the porous medium. The change of flow in space and time was observed via injection of conservative tracers and analysis of effluents. In addition, an extensive post-mortem analysis of the reacted medium was conducted. We could successfully model the flow (with and without fluid density effects) and the transport of conservative tracers with a (continuum scale) reactive transport model. The prediction of the reactive experiments initially failed. Only the inclusion of information from post-mortem analysis gave a satisfactory match for the case where the flow field changed due to dissolution/precipitation reactions. We concentrated on the refinement of post-mortem analysis and the investigation of the dissolution/precipitation mechanisms at the pore scale. Our analytical techniques combined scanning electron microscopy (SEM) and synchrotron X-ray micro-diffraction/micro-fluorescence performed at the XAS beamline (Swiss Light Source). The newly formed phases include an epitaxial growth of barite micro-crystals on large celestite crystals (epitaxial growth) and a nano-crystalline barite phase (resulting from the dissolution of small celestite crystals) with residues of celestite crystals in the pore interstices. Classical nucleation theory, using well-established and estimated parameters describing barite precipitation, was applied to explain the mineralogical changes occurring in our system. Our pore scale investigation showed limits of the continuum scale reactive transport model. Although kinetic effects were implemented by fixing two distinct rates for the dissolution of large and small celestite crystals, instantaneous precipitation of barite was assumed as soon as oversaturation occurred. Precipitation kinetics, passivation of large celestite crystals and metastability of supersaturated solutions, i.e. the conditions under which nucleation cannot occur despite high supersaturation, were neglected. These results will be used to develop a pore scale model that describes precipitation and dissolution of crystals at the pore scale for various transport and chemical conditions. Pore scale modelling can be used to parameterize constitutive equations to introduce pore-scale corrections into macroscopic (continuum) reactive transport models. Microscopic understanding of the system is fundamental for modelling from the pore to the continuum scale.