Methane‐related microbial gypsum calcitization in stromatolites of a marine evaporative setting (Münder Formation,Upper Jurassic,Hils Syncline,north Germany)

Fossil stromatolites may reveal information about their hydrochemical palaeoenvironment, provided that assignment to a specific microbial community and a corresponding biogeochemical mechanism of formation can be made. Tithonian stromatolites of the Münder Formation at Thüste, north Germany, have traditionally been considered as formed by intertidal cyanobacterial communities. However, thin sections of the stromatolites show elongated angular traces of former gypsum crystals in a dense arrangement, but no algal or cyanobacterial filament traces. Moreover, high Fe²⁺ and Mn²⁺ contents, oxygen‐isotope and sulphur‐isotope ratios of carbonate‐bound sulphates, and sulphurized hydrocarbon biomarkers of the stromatolitic carbonate indicate that CaCO₃ precipitation occurred near the oxic–anoxic interface as a result of intensive bacterial sulphur cycling rather than photosynthetic activity. Furthermore, anaerobic oxidation of methane by Archaea may have driven CaCO₃ precipitation in deeper parts of the biofilm community, as reflected by high concentrations of squalane with a strongly negative δ¹³C in conjunction with evaporite pseudomorphs showing extremely low δ¹³C_Carb ratios. Consequently, the Thüste stromatolites are now interpreted as having initially formed by gypsum impregnation of biofilms. Subsequently, early Mg‐calcitic calcitization within the biofilms occurred because of combined bacterial iron, manganese and sulphate reduction, with an increasing contribution of anaerobic oxidation of methane with depth. This model plausibly explains the prominent preservation of signals derived from oxygen‐independent metabolic pathways, whereas virtually no geochemical record exists for an aerobic community that may, nevertheless, have prevailed at the stromatolite surface. Photic‐zone stromatolites with a prominent signal of anaerobic oxidation of methane may be common in, and indicative of, oxygen‐depleted sulphate‐bearing environments with high rates of methane production, conditions that possibly were fulfilled at the Archaean to Proterozoic transition.     

Mono- and dicyclic unsaturated triterpenoid hydrocarbons in sediments from Lake Masoko (Tanzania) widely extend the botryococcene family

A mixture of C₃₃–C₃₇ botryococcenes and partially reduced derivatives was isolated from ca. 32,000 year old sediment from Lake Masoko, a freshwater crater lake in the Rungwe Range area (Tanzania). Botryococcenes and derivatives accounted for 246 μg/g dry sediment and for >92% of the hydrocarbon fraction; 1D and 2D nuclear magnetic resonance spectroscopy (NMR) and mass spectrometry allowed the structure of the dominant botryococcene (43% of hydrocarbon fraction) to be established, after purification using high performance liquid chromatography (HPLC). The compound is a novel tetraunsaturated dicyclic C₃₄ botryococcene and is named C₃₄ masokocene. Overall, the structures of six other novel botryococcenes and four partially reduced derivatives were tentatively assigned. The structures of the new biomarkers, three dicyclic C₃₄–C₃₆ botryococcenes (or masokocenes) and seven monocyclic C₃₄–C₃₇ analogues are discussed along with their biosynthetic relationship. The high abundance of such polyunsaturated compounds preserved in 32,000 year old sediment from the lake indicates an aquatic ecosystem dominated at the time by the green alga Botryococcus braunii, as well very good preservation of the organic matter.     

Surface complexation effects on phosphate adsorption to ferric iron oxyhydroxides along pH and salinity gradients in estuaries and coastal aquifers

Non-conservative behavior of dissolved inorganic phosphate (DIP) in estuaries is generally ascribed to desorption from iron and aluminum (hydr)oxides with increasing salinity. Here, we assess this hypothesis by simulating the reversible adsorption of phosphate onto a model oxide (goethite) along physico-chemical gradients representative of surface and subsurface estuaries. The simulations are carried out using a surface complexation model (SCM), which represents the main aqueous speciation and adsorption reactions of DIP, plus the ionic strength-dependent coulombic interactions in solution and at the mineral-solution interface. According to the model calculations, variations in pH and salinity alone are unlikely to explain the often reported production of DIP in surface estuaries. In particular, increased aqueous complexation of phosphate by Mg²⁺ and Ca²⁺ ions with increasing salinity is offset by the formation of ternary Mg-phosphate surface complexes and the drop in electrical potential at the mineral-water interface. However, when taking into account the downstream decrease in the abundance of sorption sites, the model correctly simulates the observed release of DIP in the Scheldt estuary. The sharp increase in pH accompanying the admixing of seawater to fresh groundwater should also cause desorption of phosphate from iron oxyhydroxides during seawater intrusion in coastal aquifers. As for surface estuaries, the model calculations indicate that significant DIP release additionally requires a reduction in the phosphate sorption site density. In anoxic aquifers, this can result from the supply of seawater sulfate and the subsequent reductive dissolution of iron oxyhydroxides coupled to microbial sulfate reduction.     

Limitations of the ferrozine method for quantitative assay of mineral systems for ferrous and total iron

The quantitative assay of clay minerals, soils, and sediments for Fe(II) and total Fe is fundamental to understanding biogeochemical cycles occurring therein. The commonly used ferrozine method was originally designed to assay extracted forms of Fe(II) from non-silicate aqueous systems. It is becoming, however, increasingly the method of choice to report the total reduced state of Fe in soils and sediments. Because Fe in soils and sediments commonly exists in the structural framework of silicates, extraction by HCl, as used in the ferrozine method, fails to dissolve all of the Fe. The phenanthroline (phen) method, on the other hand, was designed to assay silicate minerals for Fe(II) and total Fe and has been proven to be highly reliable. In the present study potential sources of error in the ferrozine method were evaluated by comparing its results to those obtained by the phen method. Both methods were used to analyze clay mineral and soil samples for Fe(II) and total Fe. Results revealed that the conventional ferrozine method under reports total Fe in samples containing Fe in silicates and gives erratic results for Fe(II). The sources of error in the ferrozine method are: (1) HCl fails to dissolve silicates and (2) if the analyte solution contains Fe³⁺, the analysis for Fe²⁺ will be photosensitive, and reported Fe(II) values will likely be greater than the actual amount in solution. Another difficulty with the ferrozine method is that it is tedious and much more labor intensive than the phen method. For these reasons, the phen method is preferred and recommended. Its procedure is simpler, takes less time, and avoids the errors found in the ferrozine method.     

Numerical estimation of REV and permeability tensor for fractured rock masses by composite element method

The Monte Carlo method is used to generate parent stochastic discrete fracture network, from which a series of fractured rock samples of different sizes and orientations are extracted. The fracture network combined with a regular grid forms composite element mesh of the fractured rock sample, in which each composite element is composed of sub‐elements incised by fracture segments. The composite element method (CEM) for the seepage is implemented to obtain the nodal hydraulic potential as well as the seepage flow rates through the fractured rock samples. The application of CEM enables a large quantity of stochastic tests for the fractured rock samples because the pre‐process is facilitated greatly. By changing the sizes and orientations of the samples, the analysis of the seepage characteristics is realized to evaluate the variation of the permeability components, the existence of the permeability tensor and the representative element volume. The feasibility and effectiveness are illustrated in a numerical example. Copyright © 2008 John Wiley & Sons, Ltd.     

Biaxial test simulations using a packing of polygonal particles

The mechanical response of cohesionless granular materials under monotonic loading is studied by performing molecular dynamic simulations. The diversity of shapes of soil grains is modelled by using randomly generated convex polygons as granular particles. Results of the biaxial test obtained for dense and loose media show that samples achieve the same void ratio at large strains independent of their initial density state. This limit state resembles the so‐called critical state of soil mechanics, except for some stress fluctuations, which remain for large deformations. These fluctuations are studied at the micro‐mechanical level, by following the evolution of the co‐ordination number, force chains and the fraction of the sliding contacts of the sample. Copyright © 2007 John Wiley & Sons, Ltd.     

Flexural isostatic response of the Alps to increased Quaternary erosion recorded by foreland basin remnants,SE France

We test the hypothesis that flexural isostatic compensation of the mass removed by enhanced Quaternary erosion is responsible for uplift of the Western European Alps and their forelands. We use two well‐preserved and well‐dated (1.8 Ma) abandonment surfaces of foreland basin remnants in SE France (the Chambaran and Valensole plateaux) as passive benchmarks for tilting of the foreland. Estimating their initial slope from morphometric scaling relationships, we determine bulk post‐depositional tilting of 0.5–0.8% for these surfaces. The calculated isostatic response of the Alpine lithosphere to erosional unloading, using the method recently proposed by Champagnac et al. [Geology 35 (2007) 195–198] , yields a predicted tilting of 0.3–0.4% in the considered areas, explaining approximately half of the determined post‐depositional tilting. Such long‐term deformation being insensitive to cyclic loading/unloading because of glaciations, we suspect the other half to be related to as yet undetermined long‐wavelength and long‐lived tectonic process(es).     

Bioaccumulation et elimination du 65Zn par Gammarus aequicauda martimov

Uptake of ⁶⁵Zn by Gammarus aequicauda results in a concentration factor of approximately 50 and it is characterised by a maximal accumulation level attained as early as the third day of the experiment. After ingestion by the gammarids of twenty contaminated meals which are distributed over a 45-day period, a transfer of ⁶⁵Zn between the food and the consumer can be observed but there is no sign of the biomagnification phenomenon. The retention rate of the radionuclide is only about 1·5% and the ⁶⁵Zn concentration in the gammarids remains markedly inferior to that of the ingested food.The elimination of the ⁶⁵Zn fixed directly from water takes place according to an exponential model which corresponds to the existence of three biological half-lives of the radionuclide, $\text{Tb}{}_1\text{? 0·5 day, Tb}{}_2\text{? 3·5 days and Tb}{}_3\text{? days}$. The excretion of ⁶⁵Zn accumulated from food is a simple exponential phenomenon which corresponds to only one biological half-life of approximately 17 days.     

Incidence de la cinetique de decroissance de la temperature apres le choc thermique sur les modifications d'activite des esterases et les possibilites de survie de Scolelepis (malacoceros) fuliginosa (annelide polychete)

Scolelepis fuliginosa reared in the laboratory at 13°C were put through 10-min thermal shocks at 16°C and 18°C and were then submitted to either a slow or a rapid temperature reduction. After the thermal shock, a posterior fragment of each specimen was cut off at intervals, until six days. Samples were submitted to electrophoresis on polyacrylamide gel, esterase activity being determined with α-naphthyl acetate.Enzymograms show that thermal shocks act on esterases in decreasing the activity of the main fractions. Immediate effects result in a very precocious enzymic response; more long-term effects depend on the maximum temperature, the animal's sex and the kinetics of the post-shock thermal reduction.Females are more sensitive than males. For a given Δt, esterase changes are greater and more long-lasting. After a 16°C Δt, a rapid decrease in temperature prevents the loss of activity of the middle and fast fractions in males and delays, by about 10 h, the alteration of female esterases. After 18°C ΔT, loss of activity of the middle and fast fractions occurs in less than 1 h, independently of the thermal kinetics, but survival is only possible—solely for males—with a rapid decrease in temperature which also delays females' deaths by between 24 and 48 h.In conclusion, a rapid decrease in temperature gives organisms a better resistance to thermal shock, as determined by esterase activity and controls the lethality of a high Δt.