Seismic and mechanical properties of Opalinus Clay: comparison between sandy and shaly facies from Mont Terri (Switzerland)

For the safe disposal of high-level radioactive waste, different host rocks are currently being considered. The favorable properties of clay are low permeability, some retention capacity concerning radionuclides, and the ability to self-seal cracks and fissures, e.g. by swelling or time-dependent compaction creep. In Switzerland, the Jurassic Opalinus Clay is envisaged as a potential host rock which—at Mont Terri—is subdivided into the sandy, shaly, and carbonate-rich facies, the latter being less abundant. For long-term safety assessments, the understanding of the relations of properties (e.g. mineralogical composition and microstructure) and performance (e.g. mechanical behavior) of clays and claystones is essential. In the case of the sandy Opalinus Clay, the mechanical strength increases with increasing carbonate content, because carbonates form the matrix. The mineralogical investigation of a set of sandy facies samples proved a significantly larger carbonate content (20–40 mass %) when compared to the shaly facies (10–20 mass %). The carbonates of the shaly Opalinus Clay, on the other hand, are mostly localized fossils aligned parallel to the bedding, acting as predetermined breaking points. Image analysis of SEM images of polished sections proved the determined microstructural differences. In addition, carbonate particles of the sandy facies are mostly isometric, whereas carbonate particles of the shaly facies cover a greater range of shapes. The mechanical tests were accompanied by investigations of the p- and s-wave velocities, which revealed that the anisotropy of the sandy facies is less pronounced than sedimentological analyses would suggest. The mechanical strength, which, for the first time, presents results of real triaxial tests of the sandy facies. The samples of the sandy facies exhibit a failure strength of σ _eff,B, approximately twice as high as was found for the shaly facies considering the deformation axis parallel to the bedding. Similar values were obtained when measuring perpendicularly to the bedding.     

Biogeochemical processes in a clay formation in situ experiment: Part E - Equilibrium controls on chemistry of pore water from the Opalinus Clay, Mont Terri Underground Research Laboratory, Switzerland

The chemistry of pore water (particularly pH and ionic strength) is an important property of clay rocks being considered as host rocks for long-term storage of radioactive waste. Pore waters in clay-rich rocks generally cannot be sampled directly. Instead, their chemistry must be found using laboratory-measured properties of core samples and geochemical modelling. Many such measurements have been made on samples from the Opalinus Clay from the Mont Terri Underground Research Laboratory (URL). Several boreholes in that URL yielded water samples against which pore water models have been calibrated. Following a first synthesis report published in 2003, this paper presents the evolution of the modelling approaches developed within Mont Terri URL scientific programs through the last decade (1997-2009). Models are compared to the composition of waters sampled during dedicated borehole experiments. Reanalysis of the models, parameters and database enabled the principal shortcomings of the previous modelling efforts to be overcome. The inability to model the K concentrations correctly with the measured cation exchange properties was found to be due to the use of an inappropriate selectivity coefficient for Na-K exchange; the inability to reproduce the measured carbonate chemistry and pH of the pore waters using mineral-water reactions alone was corrected by considering clay mineral equilibria. Re-examination of the measured Ca/Mg activity ratios and consideration of the mineralogical composition of the Opalinus Clay suggested that Ca/Mg cation exchange rather than dolomite saturation may control the ratio of these ions in solution. This re-examination also suggests that the Ca/Mg ratio decreases with increasing pore-water salinity. Several possible reasons for this are proposed. Moreover, it is demonstrated that feldspar equilibria must not be included in Opalinus Clay modelling because feldspars are present only in very small quantities in the formation and because Na/K ratios measured in pore water samples are inconsistent with feldspar saturation. The principal need to improve future modelling is additional or better data on rock properties, in particular: (i) a more detailed identification of phases in the Opalinus Clay that include redox-sensitive elements together with evaluation of their thermodynamic properties; (ii) an improved understanding of the distribution of celestite throughout the Opalinus Clay for Sr/SO₄ concentrations control; (iii) improvements in analytic and thermodynamic data for Ca-Mg rock cation exchange and mineral chemical properties and (iv) the measurement of composition and stability constants of clay minerals actually present in the formation.     

Characterization of dissolved organic matter in anoxic rock extracts and in situ pore water of the Opalinus Clay

Dissolved organic matter (DOM) from the Opalinus Clay, a potential host rock for the disposal of radioactive waste, was isolated under strictly anoxic conditions from ground rock material and compared with DOM of in situ pore water samples. For the extractions, deionized water, synthetic pore water (SPW, water containing all major ions at pore water concentrations but no organic matter) and 0.1 M NaOH were used. The influence of the solid-to-liquid ratio, extraction time, acid-pretreatment and O₂ exposure of the rock material on the isolated DOM were investigated. Liquid chromatography coupled with a total organic C detector (LC-OCD) and reverse-phase ion chromatography were used to characterize the DOM size distributions and to determine the low molecular weight organic acid (LMWOA) contents in the pore water samples and the rock extracts.The results revealed that only a small portion of the total organic C of the rock material (<0.38%) was extractable, even after removal of carbonates by acid-pretreatment. The concentrations of dissolved organic C (DOC) were found to range from 3.9 ± 0.4 to 8.0 ± 0.8 mg/L in the anoxic extracts. The pore waters exhibited similar DOC concentrations ranging from 1.2 to 15.8 ± 0.5 mg/L. The analysis by LC-OCD showed that the DOM extracted under anoxic conditions and the pore water DOM mainly consisted of hydrophilic compounds of less than 500 Da. The DOM extracted with SPW was most similar in size to the pore water DOM. Grinding the rock under oxic conditions increased the DOC yields and shifted the size distribution toward higher molecular weight compounds compared to the strictly anoxic treatment. Acetate, lactate and formate were identified in all extracts and in the pore water. In total, LMWOA accounted for 36% of the total DOC in both pore water and SPW extracts. The results imply that controlled anoxic conditions and the use of SPW as an extractant are required to isolate DOM from Opalinus Clay rocks which most resembles the in situ pore water DOM with respect to its size distribution and the LMWOA contents.     

Ageing effect on the mineral and chemical composition of Opalinus Clays (Mont Terri,Switzerland) after excavation and surface storage

Samples of Opalinus Clays from Mont Terri Underground Research Laboratory in the Swiss Jura were analyzed repetitively relative to the duration of their exposure to atmosphere. The objective was the evaluation of such a progressive exposure on the chemical composition of whole-rock samples, and on the chemical and Sr isotopic compositions of leachates obtained by leaching the rock powders with dilute acetic acid. This chemical study was complemented by scanning electron microscope observations to identify the related mineral alterations. The chemical data for the rock powders remained quite constant whatever the duration of the storage, whereas significant changes were observed for the leachates. Similar changes were observed in the leachates of samples collected progressively closer to the walls of a previously excavated niche. When storage time or distance to gallery wall increases, the main variations are: (1) a progressive decrease of the element contents and of the ⁸⁷Sr/⁸⁶Sr ratio in the leachates, (2) an alteration of pyrite followed by precipitation of Ca-sulfate in the rocks, both observed by SEM, and (3) a probable precipitation of new mineral phases in the rocks, such as Fe-oxyhydroxides and/or jarosite that could not be visualized by electron microscopic observation because of their very limited amount and very small grain size. The modifications call for an oxidation of pyrite that probably induced also an oxidation of the organic matter. It could also be shown that the reactions were enhanced by temperature increase, and that they were less pronounced in the samples behind the gallery wall than in the cores stored in laboratory conditions.     

Biogeochemical processes in a clay formation in situ experiment: Part A - Overview, experimental design and water data of an experiment in the Opalinus Clay at the Mont Terri Underground Research Laboratory, Switzerland

An in situ test in the Opalinus Clay formation, termed porewater chemistry (PC) experiment, was carried out for a period of 5 years. It was based on the concept of diffusive equilibration whereby a traced water with a composition close to that expected in the formation was continuously circulated and monitored in a packed-off borehole. The main original focus was to obtain reliable data on the pH/pCO₂ conditions of the porewater, but because of unexpected microbiologically-induced redox reactions, the objective was extended to elucidate the biogeochemical processes occurring in the borehole and to understand their impact on pH/pCO₂ and porewater chemistry in the low permeability clay formation.The behaviour of the conservative tracers ²H and Br⁻ could be explained by diffusive dilution in the clay and moreover the results showed that diffusive equilibration between the borehole water and the formation occurred within about 3 year’s time. However, the composition and pH/pCO₂ conditions differed considerably from those of the in situ porewater. Thus, pH was lower and pCO₂ was higher than indicated by complementary laboratory investigations. The noted differences are explained by microbiologically-induced redox reactions occurring in the borehole and in the interfacial wall area which were caused by an organic source released from the equipment material. The degradation of this source was accompanied by sulfate reduction and - to a lesser extent - by methane generation, which induced a high rate of acetogenic reactions corresponding to very high acetate concentrations for the first 600 days. Concomitantly with the anaerobic degradation of an organic source, carbonate dissolution occurred and these processes resulted in high pCO₂ and alkalinities as well as drop in pH. Afterwards, the microbial regime changed and, in parallel to ongoing sulfate reduction, acetate was consumed, leading to a strong decrease in TOC which reached background levels after about 1200 days. In spite of the depletion of this organic perturbation in the circuit water, sulfate reduction and methanogenesis continued to occur at a constant rate leading to near-to-constant concentrations of sulfate and bicarbonate as well as pH/pCO₂ conditions until the end of the experiment. The main sink for sulphur was iron sulfide, which precipitated as FeS (am) and FeS₂.The chemical and isotopic composition was affected by the complex interplay of diffusion, carbon degradation rates, mineral equilibria and dissolution rates, iron sulfide precipitation rates, and clay exchange reactions. The ¹³C signals measured for different carbon species showed significant variations which could only be partly explained. The main cations, such as Na, Ca and Mg remained remarkably constant during the experiment, thus indicating the strong buffering of the formation via cation and proton exchange as well as carbonate dissolution/precipitation reactions.     

Fluid inclusion, stable isotope and Ar-Ar evidence for the age and origin of gold-bearing quartz veins at Mont Chemin, Switzerland

Summary A new Swiss gold occurrence at Mont Chemin, comprising gold-bearing quartz veins, displays many characteristics that are typical of mesothermal gold deposits within the Alps and globally. The most notable of these features are: i) the presence of NaCl-H₂O-CO₂-bearing fluid with an XCO₂ of approximately 0.016 and NaCl equivalents in the range 4.6 to 10.6 weight percent, ii) greenschist formational temperatures and pressures in the range 265-285 °C and 700-1400 bars; and iii) the proximity of the occurrence to the Rhone-Simplon Line, a deep crustal structure in the Swiss Alps.Corrected Ar-Ar data for hydrothermal adularia, considered to be contemporaneous with mineral deposition from the gold-bearing fluid, yields an age of 9.9 ±1.0 Ma. Geothermal gradients and uplift rates derived from the Ar-Ar age data and the geothermometry are in agreement with existing data for this region, and indicate that the hydrothermal activity at the Mont Chemin gold occurrence records one of the last Alpine metamorphic events in the northeastern Mont Blanc massif.Temperature estimates from fluid-muscovite-quartz-feldspar equilibrium and oxygen isotope thermometry of coexisting adularia and quartz are combined with the fluid inclusion isochores to derive depositional pressures. These data yield geothermal gradients on the order of 50 °C/km and uplift rates of 0.44 mm/a for the NE portion of the Mont Blanc massif.

---

Evidenz aus Flüssigkeitseinschluß-, stabilen Isotopen- und Ar- Ar Daten fü r das Alter und den Ursprung Gold führender Quarzgänge am Mont Chemin, Schweiz

Zusammenfassung Ein neues Schweizer Goldvorkommen am Mont Chernin, es handelt sich um Goldführende Quarzgänge, zeigt viele Charakteristika, die für mesothermale Goldlagerstätten der Alpen und weltweit typisch sind: i) Die Anwesenheit von NaCl-H₂O-CO₂ Fluiden mit einem XCO₂ von ca. 0.016 und NaCl zwischen 4.6 und 10.6 Gew. % Äquiv.ii) Grünschieferfazielle Bildungstemperaturen und -drucke von 265-285°C bzw. 7001400bar. iii) Die Nähe der Vorkommen zur Rhone-Simplon Linie, einer tiefgreifenden Struktur in der Kruste der Schweizer Alpen.Korrigierte Ar-Ar Daten von hydrothermalem Adular, der als zeitgleich mit den Minerallagerstätten gebildet, angesehen wird, ergaben ein Alter von 9.9 ± 1.0 Ma. Die aus aus den Ar-Ar Daten bestimmten geothermalen Gradienten und Hebungsraten und die Ergebnisse der Geothermometrie stimmen mit bisher existierenden Daten aus dieser Region überein und zeigen, daß die hydrothermale Aktivität in den Goldvorkommen des Monte Chemin eines der letzten alpidischen metamorphen Ereignisse im nordöstlichen Mont Blanc Massiv darstellt.Temperaturabschätzungen aus Fluid-Muscovit-Quarz-Feldspat Gleichgewichten und Sauerstoffisotopen-Thermometrie an koexistierendem Quarz und Adular werden mit den Isochoren der Flüssigkeitseinschlüsse kombiniert, um die Bildungsdrucke abzuleiten. Diese Daten ergeben geothermische Gradienten in der Größenordnung von ca. 50 °C/km und Hebungsraten von 0.44 mm/Jahr für den Nordostteil des Mont Blanc Massives.

     

Hydrogeological modeling of radionuclide transport in low permeability media: a comparison between Boom Clay and Ypresian Clay

Deep low-permeability clay layers are considered as suitable environments for disposal of high-level radioactive waste. In Belgium, the Boom Clay is the reference host formation and the Ypresian Clay an alternative host formation for research and safety and feasibility assessment of deep disposal of nuclear waste. In this study, two hydrogeological models are built to calculate the radionuclide fluxes that would migrate from a potential repository through these two clay formations. Transport parameter heterogeneity is incorporated in the models using geostatistical co-simulations of hydraulic conductivity, diffusion coefficient and diffusion accessible porosity. The calculated radionuclide fluxes in the two clay formations are compared. The results show that in the Ypresian Clay larger differences between the fluxes through the lower and the upper clay boundary occur, larger total output radionuclide amounts are calculated and a larger effect of parameter heterogeneity on the calculated fluxes is observed, compared to the Boom Clay.     

Controls on stable isotope profiles in the Chalk aquifer of north-east Norfolk, UK, with special reference to dissolved sulphate

Groundwater samples were collected at a site in N Norfolk, UK, comprising a borehole penetrating Upper Chalk and piezometers open within the overlyinf glacial deposits and intervening, weathered Putty Chalk. The samples were analyzed for δ¹⁸O (water), δ³⁴S and δ¹⁸O(SO₄) and δ¹³_C(HCO₃) as well as major ions. Variations in solute concentration and isotopic composition with depth were found to be caused by limited groundwater circulation at the site and incomplete flushing of old groundwater. The isotopic data prove the existence of a mineralized palaeowater at depth, which has undergone SO₄ reduction and is being slowly modified by mixing with recent groundwater circulating at a shallow depth in a more transmissive Chalk horizon. One measured δ¹⁸O (H₂O) value of −8.25‰_vsmow represents the lightest value reported for the Norfolk Chalk aquifer and is evidence for a component of Late Pleistocene recharge trapped at depth.The wide range of observed isotope ratios at the site, e.g.δ³⁴S and δ¹⁸O SO₄ between 7.8 to 27.8‰_cdt and 5.2 to 20.0‰_ovsmow respectively, demonstrates the importance of vertical stratification of solutes and the implications this has for interpreting spatial hydrochemical surveys of groundwater.     

Faults and fractures in the Gallery 04 of the Mont Terri rock laboratory: Characterization,simulation and application

This paper deals with the reconstruction of a fracture network observed in an underground gallery of a tunnel buried in clay stones in Switzerland, below Mont Terri. The trace maps of the Gallery 04 and of the EZ-G niche of this site have first been digitized and used in various ways to characterize the data. The traces have been divided into two groups, i.e., the pre-existing faults in the gallery and the fractures of the excavated damaged zone (EDZ) in the niche. Each group has been analyzed individually. The number of data for the faults has turned out to be statistically significant, while it was very limited for the EDZ fractures. For both cases, the major statistical characteristics of the traces have been extracted and a reconstruction procedure developed and tested. A full example has been worked out; a gallery immersed in a reconstructed fractured porous medium has been meshed, and the electrical field created by a dipole at the wall calculated by solving the three dimensional Laplace equations in the fractures and in the porous medium.     

Fluid regimes in the deformation of the Helvetic nappes,Switzerland, as inferred from stable isotope data

The stable isotope composition of veins, pressure shadows, mylonites and fault breccias in allochthonous Mesozoic carbonate cover units of the Helvetic zone show evidence for concurrent closed and open system of fluid advection at different scales in the tectonic development of the Swiss Alps. Marine carbonates are isotopically uniform, independent of metamorphic grade, where ¹³C=1.5±1.5 (1 ) and ¹⁸O=25.4±2.2 (1 ). Total variations of up to 2 in ¹³C and 1.5 in ¹⁸O occur over a cm scale. Calcite in pre- (Type I) and syntectonic (Type II) vein arrays and pressure shadows are mostly in close isotopic compliance with the matrix calcite, to within ±0.5, signifying isotopic buffering of pore fluids by host rocks during deformation, and closed system redistribution of carbonate over a cm to m scale. This is consistent with microstructural evidence for pressure solution — precipitation deformation.Type III post-tectonic veins occur throughout 5 km of structural section, extend several km to the basement, and accommodate up to 15% extension. Whereas the main population of Type III veins is isotopically undistinguishable from matrix carbonates, calcite in the largest of these veins is depleted in ¹⁸O by up to 23 but acquired comparable ¹³C values. This generation of veins involved geopressurized hydrothermal fluids at 200 to 350° C where ¹⁸O H₂O=–8 to +20, representing variable mixtures of ¹⁸O enriched pore and metamorphic fluids, with ¹⁸O depleted meteoric water. Calc-mylonites ( ¹⁸O=25 to 11) at the base of the Helvetic units, and syntectonic veins from the frontal Pennine thrust are characterized by a trend of ¹⁸O depletion relative to carbonate protoliths, due to exchange with an isotopically variable reservoir ( ¹⁸O H₂O=20 to 4). The upper limiting value corresponds to carbonate-buffered pore fluid, whereas the lower value is interpreted as ¹⁸O-depleted formation brines tectonically expelled at lithostatic pressure from the crystalline basement. Carbonate breccias in one of the large scale late normal faults exchanged with infiltrating ¹⁸O-depleted meteoric surface waters ( ¹⁸O=–8 to –10).During the main ductile Alpine deformation, individual lithological units and associated tectonic vein arrays behaved as closed systems, whereas mylonites along thrust faults acted as conduits for tectonically expelled lithostatically pressured reservoirs driven over tens of km. At the latest stages, marked by 5 to 15 km uplift and brittle deformation, low ¹⁸O meteoric surface waters penetrated to depths of several km under hydrostatic gradients.     

Origin of ore fluids in the Muruntau gold system: Constraints from noble gas, carbon isotope and halogen data

Hydrothermal vein minerals directly associated with native gold mineralization in the Muruntau vein system (Uzbekistan) have been studied for noble gas, carbon isotope and halogen chemistry of the trapped ore-related fluids. Helium trapped in early arsenopyrite 1, which has preserved the original fluid signature better than associated scheelite and quartz, indicates a small input from a mantle source (?5% of total He). However, the overwhelming majority of the He in the fluid (∼95%) is from crustal sources. The noble gases Ne, Kr and Xe in the sample fluids are dominated by gases of atmospheric origin. The carbon isotope (δ¹³C: −2.1‰ to −5.3‰) and halogen characteristics of the fluids (log Br/Cl: −2.64 to −3.23) lend further support for the activity of juvenile fluids during the main ore stage. The high proportion of crustal components in the ore-forming fluids may be explained by intense fluid-rock interaction and is also supported by previous Nd and Sr isotope studies. The involvement of a juvenile fluid component during the main stage of hydrothermal activity at Muruntau (∼275 Ma) can be linked to the emplacement of lamprophyric dikes at Muruntau, due to apparently overlapping ages for high-temperature alteration, related ore vein formation and intrusion of the dikes. The input of mantle-derived fluids, possibly related to the Hercynian collisional event in the western Tien Shan, stimulated intense fluid-rock interaction in the crust. In this context, the mantle-derived fluid should be considered as one possible carrier of metals. Significant amounts of external meteoric fluids circulating in fracture systems are interpreted to have modified the noble gas signature of fluid in quartz, mostly during late, low temperature fluid circulation.     

Tracing dissolved O2 and dissolved inorganic carbon stable isotope dynamics in the Nyack aquifer: Middle Fork Flathead River, Montana, USA

The geochemistry and microbiology of shallow groundwater aquifers is greatly influenced by the concentration of dissolved oxygen gas (DO); however, the mechanisms that consume DO in groundwater (e.g., biotic or abiotic) are often ambiguous. The use of stable isotopes of molecular O₂ (δ¹⁸O-DO), in conjunction with stable isotopes of dissolved inorganic carbon (δ¹³C-DIC), has potential to discriminate between the various mechanisms causing DO depletion in subsurface waters.Here we report the results of spatial and seasonal changes in δ¹⁸O-DO and δ¹³C-DIC at the Nyack floodplain aquifer along the Middle Fork of the Flathead River near West Glacier, Montana, USA. Over a short, well constrained flow path (∼100 m) near a main recharge zone of the floodplain, the δ¹⁸O-DO consistently increased as DO concentrations decreased with distance from the recharge source. Concurrently, DIC concentrations increased and δ¹³C-DIC values decreased. These observations are explained by community respiration coupled with dissolution of calcite from cobbles in the aquifer matrix. When these results are compared to data from wells distributed over the entire floodplain (several km) a much less predictable relationship was observed between DO concentration and δ¹⁸O-DO. Many wells with low DO concentrations (e.g., <125 μmol L⁻¹ or 4 mg L⁻¹) had anomalously low δ¹⁸O-DO values (e.g., <20‰). Mass balance calculations show that approximately equal amounts of O₂ may be contributed to the aquifer by diffusion from the vadose zone and by advection from the river recharge. Calculations presented here suggest that diffusion across a narrow air-water interface can contribute isotopically light δ¹⁸O-DO to the saturated zone. Possible contributions of light δ¹⁸O-DO from other processes, such as isotopic exchange and radial oxygen loss from plant roots in or near the water table, are compared and evaluated.     

孔隙结构对低渗-特低渗砂岩储层渗流特征的影响段储层为例——以鄂尔多斯盆地东部上古生界盒8段储层为例

通过铸体薄片显微镜下观察、孔喉图像、毛细管压力、恒速压汞、气水相对渗透率、核磁共振等多种分析实验手段,研究了鄂尔多斯盆地东部上古生界盒8段低孔、低渗-特低渗砂岩储层的微观孔隙结构和渗流特征,探讨了孔隙结构对储层渗流特征的影响。结果表明,孔隙结构特征是影响低孔、低渗-特低渗砂岩储集性能与渗流特征的主要因素。而砂岩的孔隙结构特征主要受砂岩原生矿物组合与成岩演化过程及其产物的控制,盒8段各砂岩类型由于其矿物成分不同导致孔隙结构的差异,也是各砂岩类型储集性能与渗流能力存在差别的直接原因。在孔隙结构参数中,喉道的大小、有效孔隙与喉道的体积及其连通性是决定储层储集与渗流能力的关键。大孔喉对储层渗流能力的贡献更大,中-小孔喉则对储集能力的贡献相对较高。微裂缝是除孔隙结构以外影响砂岩储集性能与渗流特征的重要因素。     

High-resolution profiles of iron, manganese, cobalt, cadmium, copper and zinc in the pore water of estuarine sediment

The remobilization of iron, manganese, cobalt, cadmium, copper and zinc in the pore water of estuarine sediment cores at Yingkou was assessed using diffusive equilibrium in thin films and diffusive gradients in thin films techniques. A relatively anoxic system (+33.7 to ?224.1 mV) in the sediment cores might cause the reductive release of iron, manganese and cobalt into pore water from the estuarine sediment. High-average concentrations of iron (47.85 μg ml^?1) and manganese (3.81 μg ml^?1) were observed using diffusive equilibrium in thin films on the sediment core, but the concentration of cobalt (18.02 ng ml^?1) was relatively low. A strong correlation between iron and cobalt was observed based on the vertical profiles of the metals. Manganese and iron were more readily released from the solid phase to the solution. The peak cobalt, copper and zinc concentrations were observed in the upper layer (2–4 cm) measured using diffusive gradients in thin films. However, the peak iron, manganese and cobalt concentrations were located in the deeper layer (≥7 cm). In addition, the concentration profiles measured using diffusive gradients in thin films of cobalt, copper and zinc were independent of the iron, manganese and cobalt distribution with respect to depth.     

Assessment of the level of activity of advective transport through fractures and faults in marine deposits by comparison between stable isotope compositions of fracture and pore waters

Hydrogeology Journal - Assessment of the level of activity of advective transport through faults and fractures is essential for guiding the geological disposal of radioactive waste. In this study,...     

Oxygen isotope biogeochemistry of pore water sulfate in the deep biosphere: Dominance of isotope exchange reactions with ambient water during microbial sulfate reduction (ODP Site 1130)

Microbially mediated sulfate reduction affects the isotopic composition of dissolved and solid sulfur species in marine sediments. Experiments and field data show that the composition is also modified in the presence of sulfate-reducing microorganisms. This has been attributed either to a kinetic isotope effect during the reduction of sulfate to sulfite, cell-internal exchange reactions between enzymatically-activated sulfate (APS), and/or sulfite with cytoplasmic water. The isotopic fingerprint of these processes may be further modified by the cell-external reoxidation of sulfide to elemental sulfur, and the subsequent disproportionation to sulfide and sulfate or by the oxidation of sulfite to sulfate. Here we report values from interstitial water samples of ODP Leg 182 (Site 1130) and provide the mathematical framework to describe the oxygen isotope fractionation of sulfate during microbial sulfate reduction. We show that a purely kinetic model is unable to explain our data, and that the data are well explained by a model using oxygen isotope exchange reactions. We propose that the oxygen isotope exchange occurs between APS and cytoplasmic water, and/or between sulfite and adenosine monophosphate (AMP) during APS formation. Model calculations show that cell external reoxidation of reduced sulfur species would require up to 3000 mol/m³ of an oxidant at ODP Site 1130, which is incompatible with the sediment geochemical data. In addition, we show that the volumetric fluxes required to explain the observed data are on average 14 times higher than the volumetric sulfate reduction rates (SRR) obtained from inverse modeling of the porewater data. The ratio between the gross sulfate flux into the microbes and the net sulfate flux through the microbes is depth invariant, and independent of sulfide concentrations. This suggests that both fluxes are controlled by cell density and that cell-specific sulfate reduction rates remain constant with depth.     

Tritium corrected 14C and atmospheric noble gas corrected 4He applied to deduce ages of mixed groundwaters: Examples from the Baden region,Switzerland

Mixing of recent water (post-1953) and old water (up to a limit of 25,000 years) can be identified by tritium and ¹⁴C values. The age of an old endmember may be deduced, applying a tritium correction to the measured ¹⁴C value.⁴He may be used as a second semi-quantitative age indicator of old groundwaters, overlapping the ¹⁴C range and extending beyond it. Tritium may be used to deduce the radiogenic ⁴He concentration in the old endmember. In addition, the atmospheric noble gases may be used to check He retention and to correct for losses.The corrected ¹⁴C and ⁴He values may be used to check concordance between computed ages in mixed and unmixed groundwaters. Concordant ages indicate that the basic dating premises were not violated, whereas discordant ages indicate that secondary processes were active.The suggested approach is demonstrated for a number of springs and wells studied in the regions of Baden and Yverdon, Switzerland.     

Groundwater flow system as an archive of palaeotemperature: Noble gas, radiocarbon, stable isotope and geochemical study in the Pannonian Basin, Hungary

To establish the increase in temperature and the time span of the transition between the Late Glacial Maximum (LGM) and the Holocene, the noble gas content, ¹⁸O, ²H, ¹³C δ values, ³H and ¹⁴C activity and chemistry were studied in a groundwater flow system in Quaternary sediments in Hungary. The study area is a sub-basin of the Pannonian Basin, where the C isotope ratios are not influenced by carbonate reactions along the flow path, because the only water-rock interaction is ion exchange. The δ¹⁸O and δ²H values indicate a cold infiltration period, followed by warming, and, finally, warm temperature conditions. The noble gas data show that the average infiltration temperature was 3.3 °C in the cold, 12.9 °C in the warm, and intermediate in the transitional stage. Using the noble gas temperatures, geochemical batch modelling was performed to simulate the chemical processes. Based on the geochemical model, δ¹³C and ¹⁴C₀ (initial radiocarbon activity) in the recharging water were calculated. Transport modelling was used to simulate the distribution of chemical components, δ¹⁸O, δ²H and ¹⁴C₀, along the flow path. It was found that the main processes determining the chemical composition of the groundwater were dissolution/precipitation of calcite and dolomite during infiltration near the surface, and ion exchange along the flow path. In the recharge area the δ¹³C and ¹⁴C₀ were controlled by dissolution and precipitation of carbonate minerals, C speciation, and fractionation processes. All these processes were influenced by the recharge temperature. NGTs calculated from the dissolved noble gas concentrations showed an average of 3.3 °C for cold, and 12.9 °C for warm infiltration, i.e. for the LGM and for the Holocene. The temperature difference was thus 9.1 ± 0.8 °C, which is one of the largest degree of warming detected by noble gases so far. The alkalinity indicates that carbonate reactions were unimportant along the flow path. Owing to the temperature dependence of the equilibrium constants, temperature conditions during infiltration have to be taken into consideration in radiocarbon age calculation. Dispersive transport along the flow path modified the chemical and isotopic composition of infiltrated water. The contribution of the old pore water, which was free of the ¹⁴C isotope, resulted in uncertainties in radiocarbon age determination. It was concluded that determination of the radiocarbon age or mean residence time requires detailed knowledge of the hydraulic conditions of groundwater.