Nicole Liewig

Chemical mobilizations in laterites: Evidence from trace elements and 238U-234U-230Th disequilibria

Geochemical and mineralogical investigations, including measurements of major and trace elements, Sr isotope ratios, and 238U-234U-230Th activity ratios, were made on an old African laterite to reconstruct its formation steps and assess recent chemical mobilization. The present data support a scenario of discontinuous formation for the laterite, with different bedrock weathering conditions during the formation of each unit, rather than a scenario of continuous formation. Absolute accumulation of Fe, U, and lanthanides in the uppermost ferruginous unit suggests an autochthonous origin of this iron cap by leaching of an older overlying profile. Present chemical distributions of lanthanides, as well as of Rb, K, Ba, and Sr, within the profile cannot be linked to the mineralogical distribution of both relictual primary and authigenic secondary phases. Complementary lanthanide patterns indicate that these elements were primarily accumulated in the uppermost ferruginous unit before further remobilization and accumulation in the underlying horizons. These redistribution processes may be related to the chemical instability of the ferruginous cap. The 238U-234U-230Th disequilibria indicate that recent U mobilization occurs in the whole profile and that, as for lanthanides, there is a vertical redistribution of U from the uppermost ferruginous unit to the underlying horizons. Moreover, these data show that both U losses and gains exist at each level of the profile. A simple modeling of this double U mobilization process is proposed to interpret the 238U-234U-230Th data. Differences in the mobilization and fractionation intensities of the U input and removal processes can account for the two evolution trends, which distinguish the ferruginous unit from the underlying ones. Furthermore, on the basis of this modeling, the profile appears to be in a transient state because of recent changes in the U mobilization conditions, which could correspond to major Pleistocene climatic variations.

Rb-Sr and K-Ar Dating of Clay Diagenesis in Jurassic Sandstone Oil Reservoir, North Sea

Rb-Sr and K-Ar isotopic determinations were combined with scanning electron microscopy (SEM) observations and x-ray diffractometry (XRD) controls to date the diagenetic formation of clay minerals from oil-bearing sandstones of the Middle Jurassic Brent Sandstone in the North Sea. The separated clay fractions often contain detrital components, especially K-feldspars, which are reduced to sizes smaller than 0.4 µm either by intense in-situ alteration or by destructive sample preparation. Direct Rb-Sr and K-Ar isotopic dating of diagenetic illite therefore was not possible. Isotopic data obtained on mixtures of detrital and newly formed components showed, however, that illite formed about 40 to 45 Ma. This value also was obtained directly on clay fractions separated by a gentle method of disaggregation. Illitization is related to emplacement of hydrocarbons and associated waters into the formation. Aqueous and hydrocarbon fluids simultaneously trapped in quartz-overgrowth inclusions indicate late silicification contemporaneous with this fluid migration. Minimum trapping temperatures of at least 110°C for these fluid inclusions are too high for the present burial depth. Hot fluids are assumed to have originated in deep source rocks beneath the Brent reservoirs and migrated upward during the middle Eocene.

Dating of weathering profiles by radioactive disequilibria : contribution of the study of authigenic mineral fractions

Abstract Soil isotopic dating is important for understanding mass transfers related to rock weathering. Here we evaluate a method including TIMS analyses of (234U/238U) activity ratios on

Geochemical and K-Ar isotopic behaviour of alpine sheet silicates during polyphased deformation

Abstract Several deformational events with several generations of phengites occur in the Schistes lustres from the Northern Cottic Alps. The phengites belong mainly to 1. (1) old forms from a S1 schistosity 2. (2) deformed forms from S2 cleavage tightening zones 3. (3) neoformed forms from second-generation stretching zones. The Si-tetrahedral substitutions of these minerals, which lie between 3.28 and 3.46, depend on their microstructural site. This chemical variation cannot only be related to P-T conditions; it is also induced by deformation-related solution-deposition processes. The K-Ar apparent ages of the phengites are widely scattered between 38 and 65 Ma. The data, when plotted in an isochron diagram, suggest a two-step response (at 58—54 Ma and 50—49 Ma) of the phengites to deformation. This could happened during the same event which produced the second generation of microstructures.

Clay diagenesis in the sandstone reservoir of the Ellon Field (Alwyn, North Sea)

The nature, composition, and relative abundance of clay minerals in the sandstones of the Brent Group reservoir were studied between 3200–3300 m in a well of the Ellon Field (Alwyn area, North Sea). The sandstones have a heterogeneous calcite cement which occurred during early-diagenesis. Clay diagenesis of the cemented and uncemented sandstones was investigated using optical microscopy, scanning electron microscopy (SEM), X-ray diffraction analyses (XRD), and infrared spectroscopy (IR). The influence of cementation on clay neoformation is demonstrated in this study. Detrital illite and authigenic kaolinite are present in both the calcite-cemented and uncemented sandstones suggesting that kaolinite precipitated before calcite cementation. In the uncemented sandstones, blocky dickite replaces vermiform kaolinite with increasing depth. At 3205 m, authigenic illite begins to replace kaolinite and shows progressive morphological changes (fibrous to lath-shape transition). At 3260 m, all sandstones are not cemented by calcite. Illite is the only clay mineral and shows a platelet morphology.In the cemented samples, vermiform kaolinite is preserved at all depths, suggesting that dickite transformation was inhibited by the presence of the calcite cement. This observation suggests that calcite cement would prevent fluid circulation and dissolution-precipitation reactions.

Hydrothermal alteration of the Soultz-sous-Forêts granite (Hot Fractured Rock geothermal exchanger) into a tosudite and illite assemblage

Abstract: The Soultz-sous-Forets granitic basement represents the reservoir of an experimental Hot Fractured Rock (HFR) geothermal exchanger presently tested in the northern Rhine Graben (France), referring now to the concept of Enhanced Geothermal System (EGS). The injected fluids circulate in the natural fracture network of the granite and through its hydrothermally altered matrix. One of these fractured and altered zones, located about 800 m below the granite-sediment boundary, contains tosudite, which is a rather rare mixed-layer chlorite/smectite that crystallized here ahead of a fibrous illite/quartz/calcite paragenesis. Tosudite occurs mainly in the relics of plagioclase grains that were progressively altered by interacting with Li-bearing hydrothermal fluids percolating in the granite fractures. The age of the hydrothermal alteration activity is inferred from K-Ar dating of varied particle sizes of the associated illite: two distinct hydrothermal episodes of illite crystallization could be set at about 63 and 18-Ma or less, without further detectable precipitation, especially during the rifting of the Rhine Graben. Precipitation of fibrous illite in the pore space of the altered granite is expected to have reduced its permeability, as frequently observed in sandstone reservoirs. Clay crystallization may, therefore, represent a significant drawback for engineering the geothermal programme, as the chemical composition of the injected fluids shall be designed to reduce and even prevent illite precipitation and promote tosudite precipitation, when mixing with the natural fluids still present in the granite.

Clay ingestion enhances intestinal triacylglycerol hydrolysis and non-esterified fatty acid absorption

Consumption by animals and humans of earthy materials such as clay is often related to gut pathologies. Our aim was to determine the impact of kaolinite ingestion on glucose and NEFA transport through the intestinal mucosa. The expression of hexose transporters (Na/glucose co-transporter 1 (SGLT1), GLUT2, GLUT5) and of proteins involved in NEFA absorption (fatty acid transporter/cluster of differentiation 36 (FAT/CD36), fatty acid transport protein 4 (FATP4) and liver fatty acid binding protein (L-FABP)) was measured (1) in rats whose jejunum was perfused with a solution of kaolinite, and (2) in rats who ate spontaneously kaolinite pellets during 7 and 28 d. Also, we determined TAG and glucose absorption in the kaolinite-perfused group, and pancreatic lipase activity, gastric emptying and intestinal transit in rats orally administered with kaolinite. Glucose absorption was not affected by kaolinite perfusion or ingestion. However, kaolinite induced a significant increase in intestinal TAG hydrolysis and NEFA absorption. The cytoplasmic expression of L-FABP and FATP4 also increased due to kaolinite ingestion. NEFA may enter the enterocytes via endocytosis mainly since expression of NEFA transporters in the brush-border membrane was not affected by kaolinite. After uptake, rapid binding of NEFA by L-FABP and FATP4 could act as an intracellular NEFA buffer to prevent NEFA efflux. Increased TAG hydrolysis and NEFA absorption may be due to the adsorption properties of clay and also because kaolinite ingestion caused a slowing down of gastric emptying and intestinal transit.

Crystallization conditions of fundamental particles from mixed-layer illite-smectite of bentonites based on isotopic data (K-Ar, Rb-Sr and δ18O)

Rb-Sr and oxygen isotope studies, in addition to K-Ar isotopic determinations published previously, are reported on diagenetic and hydrothermal fundamental particles (particle thickness of 0.03 to 0.05 nm and particle ab size of 0.02–0.05 µm) of the East-Slovak Basin. The combined data set allows us to ascertain the crystallization conditions of the illite material from two bentonite units collected at two basinal sites located ~20 km apart, and characterized by prolonged diagenetic conditions induced by progressive burial. A bentonite rock characterized by a short hydrothermal event from the Zempleni mountains to the SW of the East-Slovak basin is also studied.For the two first sites, the δ18O values increase in one case and decrease in the other, when the size of the diagenetic fundamental particles from bentonite samples increases. These variations suggest that temperature increased in one and decreased in the second of the two samples collected in the basin, while the particles were growing. In the case of the hydrothermal bentonite, the δ18O values of the different size-fractions consisting of fundamental particles remain about constant, suggesting constant temperature and fluid chemistry.The Rb-Sr dates of the fundamental particles of the three bentonite rocks were systematically higher than the corresponding K-Ar ages. The 87Sr/86Sr ratios, which are initially involved in the particle nucleation, appeared higher than that of contemporaneous sea-water. In all cases, the initial 87Sr/ 86Sr ratio decreases when particle size increases, which implies supply of external Sr into the bentonite units. This external Sr seems to have had an 87Sr/86Sr ratio close or identical to that of the contemporaneous sea water. This means that Sr, probably of sea-water origin, progressively diffused from host shales into the bentonite units, during burial diagenesis. In turn it favors the suggestion made previously about diffusion of K from shales into the bentonite layers during illitization of the smectite from these units.

Interactions between ingested kaolinite and the intestinal mucosa in rat : proteomic and cellular evidences

Although some of the effects of clay ingestion by humans and animals, such as gastrointestinal wellness and the increase in food efficiency are well known, the underlying mechanisms are not yet fully understood. Therefore, the interactions between the intestinal mucosa and kaolinite particles and their effects on mucosal morphology were observed using light microscopy (LM), transmission electron microscopy (TEM), conventional (CSEM) and environmental (ESEM) scanning electron microscopy combined with an EDX micro‐analysis system. Kaolinite consumption, given with free access to rats, varied considerably from one animal to the other but was regular through time for each individual. Some kaolinite particles appeared chemically dissociated in the lumen and within the mucus barrier. Aluminium (Al) originating from ingested clay and present in the mucus layer could directly cross the intestinal mucosa. A significant increase in the thickness of the villi with large vacuoles at the base of the mucosal cells and a decrease in the length of enterocyte microvilli characterized complemented animals. The proteomic analyses of the intestinal mucosa of complemented rats also revealed several modifications in the expression level of cytoskeleton proteins. In summary, kaolinite particles ingested as food complement interact with the intestinal mucosa and modify nutrient absorption. However, these data, together with the potential neurotoxicity of Al, need further investigation.

Time-constrained illitization in gas-bearing Rotliegende (Permian) sandstones from northern Germany by illite potassium-argon dating

Permian Rotliegende sandstone cores were collected from an area of about 14,800 km2 (5710 mi2) mostly to the east-southeast of the city of Bremen in northern Germany, at depths between 4596 and 5330 m (15,079–17,487 ft). The separated size fractions (0.2, 0.2–1.0, and 1.0–2.0 m) consist of illite (90–100%) with small to minute amounts of chlorite and detectable quartz and feldspars in the coarser fractions. Scanning electron microscopic and transmission electron microscopic observations showed two types of illite morphologies: flakes coating detrital framework minerals and laths and fibers invading the pore space. The data points of most size fractions fit two isochrons, with slopes providing ages of 191 8 and 178 1 Ma, with initial 40Ar/36Ar ratios reasonably close to the atmospheric value. Microthermometric fluid-inclusion determinations in quartz and calcite characterize two types of percolating fluids: a highly saline (19% NaCl equivalent) fluid at variable temperatures depending on the reservoirs (185 to 150C) and a slightly saline one (2.6% NaCl equivalent) again at varied temperatures (170 to 145C), also depending on the locations. These temperatures are higher than paleotemperatures calculated on the basis of a present-day burial gradient of 30.5C/km, therefore favoring hydrothermal illitization, with the oldest illite crystallizing at a generally higher temperature than that of the younger illite. However, if illite coincidently precipitated with quartz, which is supported by petrographic observation, then illite with ages of about 200 Ma in the eastern to central Rotliegende sandstones of the area formed at a lower temperature but in more saline fluids than that of about 155 Ma. Alternatively, illite crystallization temperature and salinity of the interacting fluids could have been activated by the same hydrothermal activity at different locations in the studied area and could have decreased and changed, respectively, when the fluids moved in the sandstone reservoirs. The potassium-argon data fit a regional model of recurrent thermal activity, with the oldest occurrence of authigenic illite in the eastern Imbrock-Ganderkesee area and a time-dependent trend of the hydrothermal activity toward the west. Previous results from northern Germany, central Netherlands, and the southern North Sea complete the model with an initial activity at the same 200-Ma time in the western offshore and central Netherlands and an activity trend toward the east.