Paul Sardini

Large colonial organisms with coordinated growth in oxygenated environments 2.1 Gyr ago

The evidence for macroscopic life during the Palaeoproterozoic era (2.5–1.6 Gyr ago) is controversial. Except for the nearly 2-Gyr–old coil-shaped fossil Grypania spiralis, which may have been eukaryotic, evidence for morphological and taxonomic biodiversification of macroorganisms only occurs towards the beginning of the Mesoproterozoic era (1.6–1.0 Gyr). Here we report the discovery of centimetre-sized structures from the 2.1-Gyr-old black shales of the Palaeoproterozoic Francevillian B Formation in Gabon, which we interpret as highly organized and spatially discrete populations of colonial organisms. The structures are up to 12 cm in size and have characteristic shapes, with a simple but distinct ground pattern of flexible sheets and, usually, a permeating radial fabric. Geochemical analyses suggest that the sediments were deposited under an oxygenated water column. Carbon and sulphur isotopic data indicate that the structures were distinct biogenic objects, fossilized by pyritization early in the formation of the rock. The growth patterns deduced from the fossil morphologies suggest that the organisms showed cell-to-cell signalling and coordinated responses, as is commonly associated with multicellular organization. The Gabon fossils, occurring after the 2.45–2.32-Gyr increase in atmospheric oxygen concentration, may be seen as ancient representatives of multicellular life, which expanded so rapidly 1.5 Gyr later, in the Cambrian explosion.

The petrography of weathering processes: facts and outlooks

Abstract Rock weathering has been investigated from atomic to global scales through the different but complementary approaches of mineralogy, petrography, geomorphology and geochemistry. The sequences of mineral reactions involved in the alteration process are now well known. They explain the global trend of weathering phenomena but do not account for the actual rock transformation dynamics. In particular, they ignore the intimate relation of the mineral reaction progress with the increase in connected porosity. At the hand specimen scale, heterogeneity is the rule: mineral reactions are controlled by local physicochemical conditions. Alteration processes depend largely on the rock microstructure properties. They proceed through nearly-closed, semi- and completely open microsystems which are interconnected by fractures or pores. Before being leached out by the solutions which flow in the large fractures (flux), the soluble elements migrate inside the connected porosity through chemical diffusion. The dissolution of the primary minerals is mediated through local gradients of chemical potential. With increasing alteration, the rock porosity increases, as does the length of the fluid passageways and their constrictivity and tortuosity. Consequently, the apparent diffusion coefficient for the most soluble elements decreases. The amplitude of the chemical potential gradients for the most soluble elements is reduced by the progressive coating of the reactive surfaces by clays and Fe oxyhydroxides. The residence time of these elements inside the weathered rock increases as alteration progresses; an effect enhanced by their temporary adsorption on the exchangeable sites of clays and Fe oxyhydroxides. Consequently, the weathering rate decreases with time. A possible new way to calculate weathering rates could be to measure the residence time of soluble elements inside the different microsystems during their migration towards the diluted solution which occurs in the large fractures.

On the connected porosity of mineral aggregates in crystalline rocks

Abstract The 14C-PMMA impregnation of rock samples and mineral staining methods provide the connected porosity map and the spatial distribution of mineral aggregates, respectively. Combined image analysis of mineral and porosity maps allows quantification of the connected porosity distribution in rockforming mineral aggregates. After the two maps have been superimposed numerically, the 14C-PMMA method provides an indication of the extent of pore connectivity for each pixel in the analyzed area, which can be used to obtain the porosity distribution as a function of modal mineralogy. When applied to undeformed and deformed Kivetty granodiorite samples from Finland, the method allows for a detailed analysis of the rock porosity. Porosity distributions related to the undeformed rock are unimodal and approximately identical to each other. On the other hand, porosity distributions of the deformed granodiorite are multimodal and vary significantly. Constituent porosity sets of the deformed samples were albite crystals free of alkali feldspar patches and alkali feldspar phenocrysts (average porosity, Φ̅ = 0.21%), albite containing alkali feldspar patches (Φ̅ = 0.59%), rapakivi albitic mantles (Φ̅ = 1.15%), quartz (Φ̅ = 0.39%) and mafic minerals (Φ̅ = 5.8%). Moreover, the analysis indicates that the numerous micropores observed under SEM within alkali feldspar phenocrysts and albite crystals free of alkali feldspar patches are unconnected in 3D.

Interpretation of out-diffusion experiments on crystalline rocks using random walk modeling

Matrix diffusion in saturated rocks with very low permeability is one of the major mechanisms of solute transport. Laboratory out-diffusion experiments on rock samples may provide an estimate of the bulk diffusion coefficient. However, numerous results have shown that this average parameter does not really depict the complex mechanism of diffusion as a function of the internal heterogeneity of crystalline rocks. Two-dimensional images of the porosity distribution in a granite sample were obtained by impregnation with a radioactive resin and autoradiography. Some examples based on these images and synthetic images were used to perform numerical simulations of out-diffusion using two different random walk methods. The simulated shapes of the out-diffusion curves depend on the spatial distribution of the porosity and on the pore connectivity with the border of the sample. Such relations might explain the multiple nested slopes or the convex shapes often observed on real experimental curves.

A new method for quantitative petrography based on image processing of chemical element maps: Part II. Semi-quantitative porosity maps superimposed on mineral maps

Abstract Visualizing and quantifying the spatial heterogeneity of rock textures (i.e., mineral and porosity distributions) is of great interest in petrology or for understanding petrophysical properties. Spatial heterogeneities are not accurately revealed by usual techniques based on microscopy or bulk physical measurements. Detailed mineral mapping is already available from processing of chemical element maps acquired using an electron probe microanalyzer (Part I). The present paper is devoted to developing a new, coupled method for obtaining porosity maps from the same initial data. According to the difference between measured and theoretical sums of oxide weight percentages, a mean porosity is semi-quantitatively estimated for each pixel of the map (i.e., not fully absolute or accurate). All pores, including nanometer-size ones, are taken into account, whereas a sample area of several square millimeters is analyzed (spatial resolution of a few micrometers). The textural heterogeneities are thus visualized from the complementary maps of solids and voids. By superimposing these two maps, both the mean porosity and a porosity histogram associated with each rock-forming mineral are obtained. Such porosity measurements integrate the pore amounts within mono-crystals larger than the X-ray emission volume or between nanometer-size crystals of a matrix. When porosity changes are associated with a given mineral (various crystal arrangements, dissolution, etc.), pluri-modal distributions appear on porosity histograms. Thresholding each histogram mode then allows these processes to be localized. We used the MX80 bentonite to test this methodology, which represents a useful tool to study the local deformations and alteration of each rock-forming mineral, as well as to model transport properties.

Organic matter in the Soultz HDR granitic thermal exchanger (France): natural tracer of fluid circulations between the basement and its sedimentary cover

Abstract Organic matter has been observed in cores of the Soultz-sous-Forets granite (Alsace, France) at depths between 2158 and 2160 m, in a highly fractured and altered zone. The granite is overlain by a 1400-m-thick sedimentary cover containing petroleum (Pechelbronn oil field). The Soultz area is devoted to Hot Dry Rock geothermics thanks to a high geothermal gradient (up to 100 °C/km). During drilling operations, an artesian source produced oil in a fractured zone of the sedimentary cover (Buntsandstein). Its gas-chromatography and mass-spectrometry (GC-MS) analysis revealed the presence of normal alkanes (n-alkanes, i.e. linear hydrocarbons) centered on C 17 , branched alkanes with a major C 19 peak, and few unsaturated hydrocarbons. The aromatic fraction is present in small amounts. In the Soultz granite, where it is altered, organic matter is exclusively associated with tosudite (interstratified clay mineral) which crystallized in plagioclase sites during a hydrothermal alteration episode. Organic matter has been later displaced and concentrated along veinlets in which illite and carbonates have crystallized during another hydrothermal alteration stage. The soluble organic matter analyzed by GC-MS is composed of aliphatic acids, n-alkanes with a bimodal C 18 and C 24 -C 25 centered distribution, alkylbenzenes and aromatic acids. Organic compounds in the granite would either originate from a single source (immature sediments) or from two sources (immature sediments and migration of the Pechelbronn oil). No real evidence was found to prove which hypothesis is the best one. The presence of organic matter in the granite shows the importance of fluid flows between the sedimentary cover and the granitic basement through major fractures. In addition, the impregnation of plagioclase pseudomorphs with organic matter is made possible due to their high interconnection degree and to the intergranular microfracturation of the granite. The succession of several hydrothermal events with different physico-chemical characteris- tics may also be inferred from the occurrence of organic matter found in association with neoformed clay minerals in the granite.

Comparative modeling of an in situ diffusion experiment in granite at the Grimsel Test Site

An in situ diffusion experiment was performed at the Grimsel Test Site (Switzerland). Several tracers ((3)H as HTO, (22)Na(+), (134)Cs(+), (131)I(-) with stable I(-) as carrier) were continuously circulated through a packed-off borehole and the decrease in tracer concentrations in the liquid phase was monitored for a period of about 2years. Subsequently, the borehole section was overcored and the tracer profiles in the rock analyzed ((3)H, (22)Na(+), (134)Cs(+)). (3)H and (22)Na(+) showed a similar decrease in activity in the circulation system (slightly larger drop for (3)H). The drop in activity for (134)Cs(+) was much more pronounced. Transport distances in the rock were about 20cm for (3)H, 10cm for (22)Na(+), and 1cm for (134)Cs(+). The dataset (except for (131)I(-) because of complete decay at the end of the experiment) was analyzed with different diffusion-sorption models by different teams (IDAEA-CSIC, UJV-Rez, JAEA) using different codes, with the goal of obtaining effective diffusion coefficients (De) and porosity (ϕ) or rock capacity (α) values. From the activity measurements in the rock, it was observed that it was not possible to recover the full tracer activity in the rock (no activity balance when adding the activities in the rock and in the fluid circulation system). A Borehole Disturbed Zone (BDZ) had to be taken into account to fit the experimental observations. The extension of the BDZ (1-2mm) is about the same magnitude than the mean grain size of the quartz and feldspar grains. IDAEA-CSIC and UJV-Rez tried directly to match the results of the in situ experiment, without forcing any laboratory-based parameter values into the models. JAEA conducted a predictive modeling based on laboratory diffusion data and their scaling to in situ conditions. The results from the different codes have been compared, also with results from small-scale laboratory experiments. Outstanding issues to be resolved are the need for a very large capacity factor in the BDZ for (3)H and the difference between apparent diffusion coefficients (Da) from the in situ experiment and out-leaching laboratory tests.

Diffusion of Tracer in Altered Tonalite: Experiments and Simulations with Heterogeneous Distribution of Porosity

Numerical time-domain-diffusion simulations were used for studying the diffusion behavior of tracer molecules in rock matrix with homogeneous and heterogeneous porosity. As the heterogeneous sample in these simulations, a 3D tomographic image of altered tonalite was used, in which the mineral components and the pores resolved by X-ray microtomography were represented by their respective intragranular porosities determined previously by the 14C-PMMA method. The apparent diffusion coefficient of a tracer in altered tonalite was determined experimentally, and was then used in the simulations. In the altered tonalite analyzed, inclusion of heterogeneity in the porosity increased the diffusion coefficient by 16 %. Altered and pristine feldspar was the main mineral component in the sample (72 %), and it also provided the dominant contribution to tracer diffusion, explaining alone 52 % of the diffusion coefficient. The large pores resolved by microtomography (6 %) and altered and pristine mica (22 %) gave an equal contribution to the diffusion coefficient. The simulation method applied was also validated by comparing the results to both an analytical and a numerical solution to the diffusion equation in a homogenous medium. In addition, the method was compared to discrete-time random-walk simulations in the case of randomly placed overlapping spheres.

Quantification of Microscopic Porous Networks By Image Analysis and Measurements of Permeability in the Soultz-Sous-Forêts Granite (Alsace, France)

Natural or experimental fluid—rock interactions are often difficult to model theoretically because of the variability of the effective exchange surface area between the solid and the fluid. The freshest fades of the Soultz granite has been used previously for leaching experiments (Azaroual, Fouillac and Pauwels, 1993): a piece of core was crushed and leached with distilled water at 140°C, and the concentration of dissolved elements measured in the cell outflow. The computation of the distribution of the chemical species in the aqueous solution, and of their concentrations and activities with the EQ 3/6 software package (Wolery and Daveler, 1990), requires that the surface of exchange between the rock and the fluid is known. In order to match the results of the calculations with the experimental results, a 0.012 m2 g−1 exchange surface is required, whereas the exchange surface measured by BET (nitrogen adsorption) was 0.6 m2 g −1.

Primary mineral connectivity of polyphasic igneous rocks by high-quality digitisation and 2D image analysis

Abstract In order to produce accurate images for geological studies, a Canon colour laser copier CLC 300 was connected to a Silicon Graphic workstation. This connection turns the copier into a high-quality colour scanner and printer, while keeping its copier abilities. The digitised images can be processed and analysed with specific programs, written using the C language under the X-Window standard graphic environment. The basic versions of these programs can be easily modified for further developments. These tools were applied to the analyses of primary mineral connectivities in two igneous rocks: a medium-grained granite from Soultz-sous-Forets and a fine-grained tonalite from Charroux-Civray. Results are presented and discussed in terms of fluid pathway location.