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.     

Magnesium isotope systematics of the lithologically varied Moselle river basin, France

Magnesium and strontium isotope signatures were determined during different seasons for the main rivers of the Moselle basin, northeastern France. This small basin is remarkable for its well-constrained and varied lithology on a small distance scale, and this is reflected in river water Sr isotope compositions. Upstream, where the Moselle River drains silicate rocks of the Vosges mountains, waters are characterized by relatively high ⁸⁷Sr/⁸⁶Sr ratios (0.7128-0.7174). In contrast, downstream of the city of Epinal where the Moselle River flows through carbonates and evaporites of the Lorraine plateau, ⁸⁷Sr/⁸⁶Sr ratios are lower, down to 0.70824.Magnesium in river waters draining silicates is systematically depleted in heavy isotopes (δ²⁶Mg values range from −1.2 to −0.7‰) relative to the value presently estimated for the continental crust and a local diorite (−0.5‰). In comparison, δ²⁶Mg values measured in soil samples are higher (∼0.0‰). This suggests that Mg isotope fractionation occurs during mineral leaching and/or formation of secondary clay minerals. On the Lorraine plateau, tributaries draining marls, carbonates and evaporites are characterized by low Ca/Mg (1.5-3.2) and low Ca/Sr (80-400) when compared to local carbonate rocks (Ca/Mg = 29-59; Ca/Sr = 370-2200), similar to other rivers draining carbonates. The most likely cause of the Mg and Sr excesses in these rivers is early thermodynamic saturation of groundwater with calcite relative to magnesite and strontianite as groundwater chemistry progressively evolves in the aquifer. δ²⁶Mg of the dissolved phases of tributaries draining mainly carbonates and evaporites are relatively low and constant throughout the year (from −1.4‰ to −1.6‰ and from −1.2‰ to −1.4‰, respectively), within the range defined for the underlying rocks. Downstream of Epinal, the compositions of the Moselle River samples in a δ²⁶Mg vs. ⁸⁷Sr/⁸⁶Sr diagram can be explained by mixing curves between silicate, carbonate and evaporite waters, with a significant contribution from the Vosgian silicate lithologies (>70%). Temporal co-variation between δ²⁶Mg and ⁸⁷Sr/⁸⁶Sr for the Moselle River throughout year is also observed, and is consistent with a higher contribution from the Vosges mountains in winter, in terms of runoff and dissolved element flux. Overall, this study shows that Mg isotopes measured in waters, rocks and soils, coupled with other tracers such as Sr isotopes, could be used to better constrain riverine Mg sources, particularly if analytical uncertainties in Mg isotope measurements can be improved in order to perform more precise quantifications.     

Depths of Partial Crystallization of H2O-bearing MORB: Phase Equilibria Simulations of Basalts at the MAR near Ascension Island (7 11{degrees}S)

Phase equilibria simulations were performed on naturally quenchedbasaltic glasses to determine crystallization conditions priorto eruption of magmas at the Mid-Atlantic Ridge (MAR) east ofAscension Island (7–11°S). The results indicate thatmid-ocean ridge basalt (MORB) magmas beneath different segmentsof the MAR have crystallized over a wide range of pressures(100–900 MPa). However, each segment seems to have a specificcrystallization history. Nearly isobaric crystallization conditions(100–300 MPa) were obtained for the geochemically enrichedMORB magmas of the central segments, whereas normal (N)-MORBmagmas of the bounding segments are characterized by polybariccrystallization conditions (200–900 MPa). In addition,our results demonstrate close to anhydrous crystallization conditionsof N-MORBs, whereas geochemically enriched MORBs were successfullymodeled in the presence of 0·4–1 wt% H₂O in theparental melts. These estimates are in agreement with direct(Fourier transform IR) measurements of H₂O abundances in basalticglasses and melt inclusions for selected samples. Water contentsdetermined in the parental melts are in the range 0·04–0·09and 0·30–0·55 wt% H₂O for depleted and enrichedMORBs, respectively. Our results are in general agreement (within±200 MPa) with previous approaches used to evaluate pressureestimates in MORB. However, the determination of pre-eruptiveconditions of MORBs, including temperature and water contentin addition to pressure, requires the improvement of magma crystallizationmodels to simulate liquid lines of descent in the presence ofsmall amounts of water. KEY WORDS: MORB; Mid-Atlantic Ridge; depth of crystallization; water abundances; phase equilibria calculations; cotectic crystallization; pressure estimates; polybaric fractionation     

Structural investigation of the synthetic CaAn(PO4)2 (An = Th and Np) cheralite-like phosphates

The crystallographic structures of the synthetic cheralite, CaTh(PO₄)₂, and its homolog CaNp(PO₄)₂ have been investigated by X-ray diffraction at room temperature. Rietveld analyses showed that both compounds crystallize in the monoclinic system and are isostructural to monazite LnPO₄ (Ln = La to Gd). The space group is P2₁/n (I.T. = 14) with Z = 2. The refined lattice parameters of CaTh(PO₄)₂ are a = 6.7085(8) Å, b = 6.9160(6) Å, c = 6.4152(6) Å, and β = 103.71(1)° with best fit parameters R _wp = 4.87%, R _p = 3.69% and R _B = 3.99%. For CaNp(PO₄)₂, we obtained a = 6.6509(5) Å, b = 6.8390(3) Å, c = 6.3537(8) Å, and β = 104.12(6)° and R _wp = 6.74%, R _p = 5.23%, and R _B = 6.05%. The results indicate significant distortions of bond length and angles of the PO₄ tetrahedra in CaTh(PO₄)₂ and to a lesser extent in CaNp(PO₄)₂. The structural distortions were confirmed by Raman spectroscopy of CaTh(PO₄)₂. A comparison with the isostructural compounds LnPO₄ (Ln = Ce and Sm) confirmed that the substitution of the large rare earth trivalent cations with Ca²⁺ and Th⁴⁺ introduces a distortion of the PO₄ tetrahedra.     

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).     

Potentiometric determination of calcium and magnesium in seawater

Methods are described for the complexometric determination of calcium and magnesium in seawater, using an amalgamated silver electrode for end-point detection. In the presence of a small amount of mercury(II)-chelonate, the amalgamated silver electrode serves as a pM indicator during the complexometric titration, the Hg complex being stronger than Ca, Mg and Sr complexes. Calcium is determined by titration with EGTA, calcium+magnesium+strontium by titration with EDTA and magnesium is obtained by difference. Average values of 0.02120 (standard deviation 0.00004) for Ca:Cl‰ and 0.06671 (standard deviation 0.00014) for Mg:Cl‰ were obtained for samples from tropical North Atlantic Ocean.     

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.