Mineralogical and isotopic record of biotic and abiotic diagenesis of the Callovian-Oxfordian clayey formation of Bure (France)

The Callovian-Oxfordian (COx) clayey unit is being studied in the Eastern part of the Paris Basin at depths between 400 and 500 m depth to assess of its suitability for nuclear waste disposal. The present study combines new mineralogical and isotopic data to describe the sedimentary history of the COx unit. Petrologic study provided evidence of the following diagenetic mineral sequence: (1) framboidal pyrite and micritic calcite, (2) iron-rich euhedral carbonates (ankerite, sideroplesite) and glauconite (3) limpid calcite and dolomite and celestite infilling residual porosity in bioclasts and cracks, (4) chalcedony, (5) quartz/calcite. Pyrite in bioturbations shows a wide range of δ³⁴S (−38‰ to +34.5‰), providing evidence of bacterial sulphate reduction processes in changing sedimentation conditions. The most negative values (−38‰ to −22‰), measured in the lower part of the COx unit indicate precipitation of pyrite in a marine environment with a continuous sulphate supply. The most positive pyrite δ³⁴S values (−14‰ up to +34.5‰) in the upper part of the COx unit indicate pyrite precipitation in a closed system. Celestite δ³⁴S values reflect the last evolutionary stage of the system when bacterial activity ended; however its deposition cannot be possible without sulphate supply due to carbonate bioclast dissolution. The ⁸⁷Sr/⁸⁶Sr ratio of celestite (0.706872-0.707040) is consistent with deposition from Jurassic marine-derived waters. Carbon and oxygen isotopic compositions of bulk calcite and dolomite are consistent with marine carbonates. Siderite, only present in the maximum clay zone, has chemical composition and δ¹⁸O consistent with a marine environment. Its δ¹³C is however lower than those of marine carbonates, suggesting a contribution of ¹³C-depleted carbon from degradation of organic matter. δ¹⁸O values of diagenetic chalcedony range between +27‰ and +31‰, suggesting precipitation from marine-derived pore waters. Late calcite crosscutting a vein filled with chalcedony and celestite, and late euhedral quartz in a limestone from the top of the formation have lower δ¹⁸O values (∼+19‰), suggesting that they precipitated from meteoric fluids, isotopically close to present-day pore waters of the formation. Finally, the study illustrates the transition from very active, biotic diagenesis to abiotic diagenesis. This transition appears to be driven by compaction of the sediment, which inhibited movement of bacterial cells by reduction of porosity and pore sizes, rather than a lack of inorganic carbon or sulphates.     

Characterization and correlation of Upper Jurassic (Oxfordian) bentonite deposits in the Paris Basin and the Subalpine Basin, France

Abstract Explosive volcanic activity is recorded in the Upper Jurassic of the Paris Basin and the Subalpine Basin of France by the identification of five bentonite horizons. These layers occur in Lower Oxfordian (cordatum ammonite zone) to Middle Oxfordian (plicatilis zone) clays and silty clays deposited in outer platform environments. In the Paris Basin, a thick bentonite (10–15 cm), identified in boreholes and in outcrop, is dominated by dioctahedral smectite (95%) with trace amounts of kaolinite, illite and chlorite. In contrast, five bentonites identified in the Subalpine Basin, where burial diagenesis and fluid circulation were more important, are composed of a mixture of kaolinite and regular or random illite/smectite mixed-layer clays in variable proportions, indicating a K-bentonite. In the Subalpine Basin, a 2–15 cm thick bentonite underlain by a layer affected by sulphate–carbonate mineralization can be correlated over 2000 km². Euhedral zircon, apatite and biotite crystals have been identified in all the bentonites. The geochemical composition of the bentonites in both basins is characterized by high concentrations of Hf, Nb, Pb, Ta, Th, Ti, U, Y, Zr and low concentrations of Cr, Cs and Rb. Biostratigraphical and geochemical data suggest that the thick bentonite in the Paris Basin correlates with the thickest bentonite in the Subalpine Basin, located 400 km to the south. These horizons indicate that significant explosive volcanic events occurred during the Middle Oxfordian and provide potential long-distance isochronous marker beds. Immobile element discrimination diagrams and rare-earth element characteristics indicate that the original ash compositions of the thickest bentonites correspond to a trachyandesitic source from a within-plate alkaline series that was probably related to North Atlantic rifting.     

Chlorine transfer out of a very low permeability clay sequence (Paris Basin, France): Cl and Cl evidence

The marine Callovo-Oxfordian clay formation is found at a depth around 410m in the eastern part of the Paris Basin (France). It is a very low permeability formation investigated by the French agency for nuclear waste management (ANDRA) to study the feasibility of a radioactive waste disposal. Examining hydrogeological and geochemical characteristics of the clay sequence may test confinement properties of this formation. This study uses chlorine isotopes to investigate long-term transport processes which may carry chemical elements out of the clay layer to the surrounding rocks. Detailed chlorine concentration and δ³⁷Cl depth profiles are examined using pore waters and aquifer waters sampled in the clay formation and its surrounding aquifers (the Dogger at the bottom and the Oxfordian/Kimmeridgian/Tithonian unit at the top). They are discussed in terms of chlorine budget and hydrogeological processes.Clay pore waters and aquifer waters show strong chlorine concentration depletion (<3000 mg/L) relative to the original marine interstitial water (∼19000 mg/L). This probably results from an early dilution by meteoric water in limestones (as also indicated by oxygen and hydrogen isotopes).A steep Cl-concentration gradient from the Dogger at ∼500m in depth (∼2500 mg/L) to the Oxfordian/Kimmeridgian/Tithonian aquifer near the surface (≈ 10 mg/L) is associated to a ‘v-shaped’ profile of the δ³⁷Cl values. Modelling Cl transport shows that a hydrodynamic dispersion process explains Cl concentration and δ³⁷Cl profiles in Oxfordian Limestone. This process implies a mean upward flux of chloride in the 2.6 10⁻⁸-8.2 10⁻⁸ mole/m²/yr range from the clay formation towards upper limestones where a westward advective flow disperses the chloride. The modelling and knowledge of underground water transfer suggest a maximum effective Cl-hydrodynamic vertical dispersion coefficient (= vertical Cl-transport coefficient) of ∼7.6 10⁻¹⁰ m²/s.Chlorine transfer through the Callovo-Oxfordian clay, since deposition 160My ago, can be mainly described by the interplay of an early dilution and a later hydrodynamic dispersion event which has apparently erased most of the isotopic effects of diagenetic events (such as early diffusion, ion filtration etc.).     

Classifying chalk microtextures: Sedimentary versus diagenetic origin (Cenomanian–Santonian,Paris Basin,France)

Microtexture describes the type of particles and their arrangement in matrix samples at scanning electron microscopy scale. Although a microtexture classification exists for micritic limestone, it cannot be directly applied to chalk. This study therefore proposes a classification of chalk microtextures and discusses the origin of microtexture variability. Chalk was sampled at thirteen spatio‐temporal locations along the coastline of northern France (Cenomanian–Santonian). Four criteria are defined to describe, characterize and determine chalk matrix microtexture: (i) mineralogical content; (ii) biogenic fraction; (iii) micritic fraction; and (iv) cement fraction. From these criteria, two major groups are defined: Pure Chalk Microtexture Group, with seven classes, and Impure Chalk Microtexture Group, divided into two subgroups: Argillaceous Microtexture with four classes and Siliceous Microtexture with two classes. Microtexture variability is related both to initial sedimentation and to diagenesis. Sedimentological conditions (for example, climate and distance from shore) affect chalk composition (carbonate content and type of insoluble particles), thus influencing microtexture. Changes in Pure Chalk Microtexture are the result of increasing diagenetic intensity. This classification can also be used to characterize the microtexture of subsurface chalk reservoirs. Reservoir quality depends on the petrophysical and mechanical properties of reservoir rocks, which can be better understood by exploring their sedimentary and diagenetic history, revealed by the study of chalk microtexture variability.     

Correlation of reefal Oxfordian episodes and climatic implications in the eastern Paris Basin (France)

Oxfordian reefal episodes of Lorraine and Burgundy have a long time been considered as contemporaneous. Biostratigraphic data and sequential evolutions peculiar to each region indicate their structural autonomy during Oxfordian times. A north‐south‐oriented well‐logging transect shows that, during the Middle Oxfordian, a shallow reefal platform developed in Lorraine while thin deeper deposits occurred in Burgundy. In spite of their different ages, reefal episodes of Middle Oxfordian in Lorraine and Upper Oxfordian in Burgundy exhibit a broadly similar vertical evolution of coral communities. During the Late Oxfordian, the contemporaneous occurrence of a diversified assemblage in the Burgundy region, a colder coral assemblage characterized by eurytopic genera and the decrease in seawater isotopic temperatures in Lorraine can be explained by a shift in trophic conditions, a climatic change related to structural rearrangements in this strategic place and a modification of oceanic circulations between the arctic and the Tethyan regions.     

Depositional environments and iron ooid formation in condensed sections (Callovian–Oxfordian, south-eastern Paris basin, France)

Carbonate platforms across Western Europe were superseded at the Middle–Upper Jurassic (Callovian–Oxfordian) boundary either by alternating marl–limestone and widespread marl deposits or by condensed sections containing iron ooids. The characteristics of marine condensed sections in the south-eastern part of the Paris Basin (France) and their distribution pattern are examined here, and a model of iron ooid formation is developed. Iron ooids are found from the shoreface to the offshore zone. They are most abundant in the median-to-distal offshore transition zone, where they originally formed. They also occur commonly, albeit often as reworked grains, in the proximal offshore zone, to which they were transported. The contemporaneous, thick, predominantly marl sections that occur laterally are devoid of iron ooids and were deposited in deeper settings (distal offshore zone). The iron ooids are composed of goethite. Typically, they have a nucleus made up of a clump of goethite crystals and a laminated cortex. Three distinctive nanostructures are identified in the cortex laminae: (i) a nanograined crystalline structure typical of primary goethite; (ii) a secondary nanoflaked structure thought to have formed mechanically by reorientation of the goethite crystals; and (iii) a coalesced structure acquired by subsequent diagenetic recrystallization. The iron ooids formed successively (i) by lamina growth when goethite precipitated in the surface layer of the sediment (nanograined structure) and (ii) by interruption of growth when the ooids were remobilized by hydrodynamic agents, as reflected by the flaked nanostructure; (iii) these two nanostructures were sometimes transformed into a coalesced structure by recrystallization when ooids were buried.     

Stable isotope contents of porewater in a claystone formation (Tournemire, France): assessment of the extraction technique and preliminary results

Claystones are one of the types of geological formations that are considered for the isolation of radioactive wastes. The study of water transfer through these rocks comes up against a lot of difficulties. Among them is the problem of extracting representative samples of interstitial water from indurated claystones with very low water contents (usually less than 10% vol.). The vacuum distillation technique considered here for samples from the Tournemire site (Toarcian argillite formation), is one of the few usable techniques to extract water from this type of rock in order to perform stable isotope investigations on porewater. Tests have shown that the isotope water content is not only influenced by the yield of extraction and the temperature of distillation (as already known), but also by the rain size and the contact time between the crushed sample and the atmosphere. This affects particularly¹⁸O data.The first isotopic results on the Tournemire claystones suggest a meteoric origin for its interstitial water. Data show a depletion in heavy isotopes with respect to present day meteoric water, that could suggest a recharge under climatic conditions cooler than at present. A clear link appears between the isotope contents of water and the structural context: interstitial waters of rock samples taken in the fractured zone of the massif seem to have been affected by a secondary process (evaporation or water-rock exchange) leading to the enrichment in heavy isotopes.     

Groundwater dolocretes in a lake-marginal environment: an alternative model for dolocrete formation in continental settings (Danian of the Provence Basin, France)

In the long continental history of the Provence Basin which extended from Santonian to Oligocene times, a major period of palaeosol development occurred in the Danian. Dolocretes developed within floodplain silts, and partly from palustrine limestones. Dolocretes are overlain by pedogenic facies: calcretes and palustrine limestones. Gradational lower and upper limits of profiles, succession of nodular, coalescent and massive horizons, the epigenesis of quartz by dolomite, the unimodal crystal size and the euhedral dolomite fabric, as well as the absence of biogenic structures and vadose cements show that dolocretes formed in the phreatic zone. The exclusive occurrence of dolocretes around the palaeolake or playa suggests that dolocrete formed by the mixing of groundwaters and lake brines, which infiltrated the phreatic zone during periods of strong evaporation and lake level lowering. The term halo dolocrete is proposed to describe this type of dolocrete deposit. Subsequent alteration of the dolocrete includes leaching of the central core of dolomite crystals and calcitization. Calcitization was either fabric-destructive (type I) or fabric-preserving (type II) and took place during very early diagenesis, i.e. concomitant with calcrete formation or palustrine limestone deposition. Fabric-destructive calcitization is attributed to a drop in the lake level, when the upper part of the dolocrete was subjected to vadose zone processes, whereas the fabric-preserving calcitization resulted from reactions with dilute lake and groundwaters during rise in lake level.     

Geochemistry and origins of natural gases in the central Junggar Basin,northwest China

The petroliferous central Junggar Basin in northwest China is predominantly an oil exploration region. However, its gas exploration also might have good prospects. Thus to assist in gas exploration, the geochemistry and origins of gases are discussed in this paper based on relatively comprehensive analyses of compositions, carbon isotopes and light hydrocarbons of gases. Based on the results, the gas genetic types are grouped into families and combined with the geological setting (e.g., biomarkers of retrograde condensates and source rock characteristics). We show that there are four representative genetic types of gases. The first consists of gases derived from Permian lacustrine mudstones with type I–II kerogen and type III kerogen sources in the Penyijingxi sag. Their representative geochemical feature is δ¹³C₂ ranging from −31.4‰ to −24.7‰. The second is gas sourced from Carboniferous tufaceous mudstones of type III kerogen in the Dishuiquan sag, whose representative geochemical feature is the heaviest values of δ¹³C₁ in the studied samples, ranging from −32.0‰ to −30.4‰. The third consists of gases sourced from Jurassic coals and mudstones in the Shawan–Fukang sag. The light hydrocarbon fingerprints of these gases are similar to those of gases and oils typically derived from Jurassic source rocks in the southern Junggar Basin. The fourth is gas most likely generated from the degradation of crude oil. It is mainly found in the Luliang area and has dryness values as much as 0.999 and δ¹³C₁ ranging from −54.8‰ to −43.2‰. Among these four types of gases, the first (mainly sourced from the Permian lacustrine mudstones in the Penyijingxi sag) is the predominant type.     

The Permo-Carboniferous Saar-Nahe Basin,south-west Germany and north-east France: basin formation and deformation in a strike-slip regime

The Permo-Carboniferous Saar-Nahe Basin in south-west Germany and north-east France formed at the boundary between the Rhenohercynian and Saxothuringian zones within the Variscan orogen, where non-marine sediments were deposited in a narrow, structurally controlled basin. The basin has an asymmetrical geometry perpendicular to the South Hunsruck Fault. However, there is a lack of growth of the sediment pile into the fault, and isopach maps show the depocentre always located adjacent to the South Hunsrück Fault, but migrating towards the north-east with time. This pattern is typical of a strike-slip basin, indicating that the South Hunsruck Fault was a dextral strike-slip fault during sedimentation. Tectonic subsidence curves indicate that, during the Middle Devonian to Early Carboniferous, the basin subsided due to thermal relaxation of the lithosphere. A change to very rapid subsidence at the start of the Westphalian continued until late in the Autunian. This was due to mechanical subsidence associated with strike-slip movement on the South Hunsruck Fault. Towards the end of subsidence in the Saar-Nahe Basin, the Grenzlager volcanics introduced a thermal pulse into the crust, leading to thermal cooling and relaxation of the lithosphere.     

Non-aromatic biomarkers associated with a Palaeogene salt formation (Bresse, France)

This study provides information on non-aromatic hydrocarbons contained in thick Palaeogene halite sequences in the Bresse region (France). The presence of almost uniquely biological markers and the absence of thermogenic compounds denote the low maturity of the corresponding samples consistent with Rock-Eval pyrolysis data. The distribution of n-alkanes enables the distinction of three main biological signatures: algal (mode in nC17–nC18); terrestrial (mode in nC29–nC31) and bacterial (mode in nC25–nC26 with no odd-even carbon number predominance). As to the cyclic biomarkers, hopanes and hopenes are largely predominant over steranes and diasterenes in samples having received appreciable amounts of terrestrial inputs (Type B) and conversely for the samples containing high proportions of algal debris (Type A, Type C).     

Metasomatism and graphite formation at a lithological interface in Malaspina (Alpine Corsica, France)

Multiple pieces of geologic evidence suggest that interfaces between contrasted lithologies exert a strong control on the fate of volatiles in subduction zones. Here we present results from a contact between serpentinites and sediments, located in Corsica and metamorphosed in the blueschist facies during the alpine orogeny. It was shown previously that carbonates in the sediments have been reduced to graphitic carbonaceous material within a 5–10-cm-thick reaction zone at the contact with serpentinites. In an effort to investigate the mechanisms governing this unusual process, bulk rock geochemical analyses incorporating a statistical analysis of compositional data are presented. Observations show that the fate of C was decoupled from that of other elements such as O, H, and large-ion lithophile elements—e.g. K, Sr, Ba...,As—that were extensively leached from the reaction zone. Notably, Na is strongly enriched in the reaction zone and structurally linked to pectolite. Reducing conditions, manifested by the depletion of O in the reaction zone compared to the bulk metasediment, were likely maintained by the presence of Fe(II) in the serpentinite. Moreover, thermodynamic calculations show that the low solubility of carbon in COH fluids at high-pressure and low-temperature conditions was the main driver for graphite precipitation synchronously with carbonate destabilization. This may have been kinetically favored by the presence of already existing graphitized carbonaceous material and phengite in the metasediment. Limited lateral flow might have contributed as well to the geochemical and petrological patterns observed in these rocks.     

Measurement of natural stresses in a Provence mine (Southern France)

Stress measurements were carried out in the Arc syncline using drifs in a lignite mine. Eleven sites were investigated using the flat jack and hydraulic fracturing (or stimulating) methods. Two stress states were found to coexist, one isotropic, the other highly anisotropic. The orientations of the principal stresses are not homogeneous and an orientation ranging from E-W to NE-SW predominates locally. This does not accord with the regional stress field. The vertical stresses are systematically underestimated.     

Evaluation of heavy metal bio-availability from Almagrera pyrite-rich tailings dam (Iberian Pyrite Belt,SW Spain) based on a sequential extraction procedure

The beginning of polymetallic sulphide ore exploitation at Almagrera, Iberian Pyrite Belt, SW Spain, has been dated back to pre-Roman times; mining activity lasted until 2001 when it was definitely halted. The Almagrera sulphide tailings dam was built at the Sotiel–Coronada mine, where Cu, Zn and Pb concentrates were obtained by flotation processes, and sulphide (mainly pyrite) wastes formed. The dam was built as a water-reservoir, on a tectonic fault; its hazard is currently documented by the released wastes after a strong storm in the region, then, its stability is not monitored by the owner.     

Groundwater dolocretes from the Upper Triassic of the Paris Basin, France: a case study of an arid, continental diagenetic facies

Thick dolomite-cemented horizons (dolocretes) occur within a fluvial sandstone-mudstone sequence of Late Triassic age in the western part of the Paris Basin, France. Two types of dolomites can be distinguished: (a) nodular dolomitic beds less than a few metres thick, which formed within mottled overbank siltstones and mudstones; and (b) massive dolomite up to 16 m thick, which occurs in coarse grained channel sandstones and conglomerates. The majority of the dolomite consists of a finely crystalline groundmass of dolomicrospar and, less commonly, dolomicrite. Glaebules, irregular spar-filled cracks, spheroidal dolomite, silicification and vuggy porosity are locally abundant in the massive dolomite. In contrast, biologically induced micromorphological features such as rhizocretions and alveolar-septal fabrics were observed in the thin, nodular dolomite beds. The dolomite is near stoichiometric, well ordered and non-ferroan. 18O values range from ?7·7 to ?0·4%o PDB and 18O values range from ?5·1 to + 1·8%0 PDB and no obvious difference in the stable isotopic composition between both types of dolomites was observed. Sr isotope ratios range from 0·7101 to 0·7126 and are invariably higher than the contemporary Triassic sea water. A vadose—pedogenic origin for the thin dolocrete layers is indicated by the occurrence of rhizocretions and other biological structures. Several features, however, argue against a pedogenic origin for the massive carbonates, most notably the absence of biologically induced structures, the occurrence in coarse grained channel (and not overbank) deposits, and the great thickness. These units are thus interpreted as groundwater in origin. Phreatic calcretes of Quaternary age, widespread in inland Australia, are regarded as a modern analogue for the Triassic Paris Basin dolocretes. Petrographic observations argue in favour of primary (proto)dolomite precipitation, although early diagenetic replacement of calcite by (proto)dolomite cannot be ruled out. Strontium and carbon isotope data of early diagenetic dolocrete cements and oxygen isotope data of early diagenetic silica indicate an entirely non-marine, continental origin for the groundwaters. The poorly ordered and non-stoichiometric protodolomite probably underwent stabilization upon further burial resulting in a near-stoichiometric, well ordered dolomite that clearly lacks evidence for pervasive recrystallization.     

The Vigny limestones: a record of Palaeocene (Danian) tectonic-sedimentary events in the Paris Basin

Danian marine sedimentation in the Paris Basin occurred between two major erosional phases. The earlier was responsible for the stripping of presumably deposited Maastrichtian sediments and of a variable thickness of Campanian chalk. The later occurred during the late Palaeocene and resulted in the erosion of almost all Danian deposits, which are now limited to small and scattered outcrops. One of these outcrops corresponds to reefal and peri‐reefal limestones of middle to late Danian age, exposed in the quarries of Vigny (NW of Paris). Danian deposits here show intricate relations with the surrounding Campanian chalk. Danian sedimentation was contemporaneous with faulting, which generated signifiant sea‐floor relief and resulted in contrasting depositional areas: topographic highs with coralgal reefs, and depressions where calcirudite channel fill accumulated. Normal faulting occurred along WNW–ESE master faults. The generation of submarine fault scarps gave rise to various types of gravity‐driven phenomena, including the sliding and slumping of large blocks of reefal limestone and the deposition of carbonate debris flows. Along with the redeposition of the Danian carbonates, flows of fluidized and reworked Campanian chalk resulted from the peculiar physical properties of the undercompacted chalks. Erosion and faulting occurred predominantly during the Palaeocene and represent a major episode in the physiographic evolution of the Paris Basin.     

Sequential extraction procedure in columns. Part 1: Development and description of a new method

A sequential extraction procedure was carried out in columns using reagents that are known to be reliable from batch tests. The intention was to distinguish between different chemical forms of iron and heavy metals in samples from reduced porous aquifers, which demands anaerobic conditions for the extraction procedure and the determination of small amounts of reactive mineral phases in a quartz dominated sediment system. By means of the developed method, anaerobic conditions can be guaranteed in the columns, which could not be realized to full satisfaction in batch tests that were carried out in a glove box. In order to distinguish between the fractions that were water soluble, exchangeable, bound to carbonates and bound to hydroxides, different reagents were pumped through the sediments and sampled after passage of the columns. Sediment samples of 10 kg each were investigated in this way. The extraction steps were known to be complete when analyses revealed that no further major and trace elements were leached out of the columns. This approach enabled well-adjusted amounts of reagents to be used. By means of the sequential extraction procedure in columns the composition of even small amounts of reactive mineral phases can be determined successfully, which contributes to a deeper understanding of the hydrogeochemical processes in aquifers. In batch tests this accuracy cannot be reached because of the surplus of the extraction solution in relation to the amount of sediment (higher solution-sediment ratio). Furthermore, larger samples are much more representative of the composition of the aquifers than smaller ones and the heterogeneity of the sediment does not limit the accuracy of the results as much as in batch tests. In addition, the technique of flushing sediment in a column is much more typical for the situation in an aquifer than suspending a few grams of a sample in the extracting reagents in batch extraction tests. In order to demonstrate the methodical improvements and field applications, the newly developed method was used to investigate the changing binding forms and mobility of iron and trace metals in samples from a lignite overburden dump, which are influenced by pyrite oxidation processes (acidification) followed by the addition of crushed limestone (neutralization) (see "Sequential extraction procedure in columns. Part 2: Application of a new method").     

A study of natural site formation processes in the Kortallayar Basin,Tamil Nadu,South India

This article presents the results of a study of natural processes influencing the formation of Palaeolithic sites, in a ferricrete landscape, in the Kortallayar basin, Tamil Nadu, South India. The principal points discussed here include the Quaternary geomorphology and Palaeolithic archaeology of the region and the methodology used for the study of site taphonomy. As a result of this research, Palaeolithic sites were categorized into several types based on their sedimentary context, artefact spatial distribution, and morphology and degree of integrity. This work is the first of its kind in establishing a methodology for the study of Palaeolithic sites in ferricrete landscapes in India. The results of this research may be relevant to understanding the study of formation processes at sites in similar contexts elsewhere in the Subcontinent. © 1999 John Wiley & Sons, Inc.     

Modeling the composition of the pore water in a clay-rock geological formation (Callovo-Oxfordian, France)

The interstitial water contained in the microporosity of highly compact clay-rich media does not obey the classical condition usually used to derive the ionic composition of a solution. This is because the requirement for global electroneutrality of a charged microporous body (one having a significant fraction of pores with dimensions of the same order of size as the diffuse double layer) implies that the net charge density of the pore water must balance the deficiency (or the excess) of electrical charge carried by the solid matrix. In order to determine the solution composition in the micropores of a clay-rock, we first generalize the Donnan equilibrium conditions for the case of a multi-ionic electrolyte, with partitioning of the charge compensating counterions between the Stern and the diffuse layers A material-specific geochemical equilibrium model, incorporating an electrical triple layer model for adsorption reactions, is used to calculate the partition coefficient for the compensating ion charge (i.e., the fraction of charge in the Stern layer). This is then used to calculate the osmotic pressure and ionic composition of the pore water in the micropores. The material considered in this study is the argillite clay-rock sampled from the Callovo-Oxfordian geological formation under consideration in France for a deep geological disposal facility for radioactive waste.