The measurement of D/H ratio in alkenones and their isotopic heterogeneity

Previous paleoenvironmental studies reported the δD values of a mixture of coeluting alkenones. Here, we present a semi-preparative normal-phase high-performance liquid chromatography–mass spectrometry (NP-HPLC–MS) method for purifying long chain (C₃₇ and C₃₈) unsaturated methyl and ethyl ketones (alkenones) on the basis of chain length and degree of unsaturation.The method was applied to purify alkenones in suspended particles and surface sediments from a site in Chesapeake Bay, eastern USA. The hydrogen isotopic composition of di- and triunsaturated C₃₇ and C₃₈ alkenones differed significantly on the basis of chain length and the degree of unsaturation, demonstrating the importance of gas chromatography–isotope ratio-mass spectrometry (GC–irMS) analysis of individual alkenones for accurate paleoenvironmental reconstruction. Constant fractionation factors between alkenones with different chain length but the same degree of unsaturation (${\alpha }_{{\text{C}}_{37:2}''–''{\text{C}}_{38:2}}\text{and}{\alpha }_{{\text{C}}_{37:3}''–''{\text{C}}_{38:3}}=1.01$) and those with the same chain length but different degree of unsaturation (${\alpha }_{{\text{C}}_{37:2}''–''{\text{C}}_{37:3}}\text{and}{\alpha }_{{\text{C}}_{38:2}''–''{\text{C}}_{38:3}}=0.97$) in all samples suggest that the values may represent hydrogen isotope fractionation associated with elongation and desaturation during alkenone biosynthesis.     

Bulk modulus of Fe-rich olivines corrected for non-hydrostaticity

In situ X-ray diffraction was used to measure the isothermal bulk modulus at room conditions (K_T0) of synthetic olivines with different iron contents. The chemical formulae of the olivine samples were ${({\mathrm{Fe}}_x,{\mathrm{Mg}}_{1?x})}_2\mathrm{Si}{\mathrm{O}}_4$ with x = 0.45; 0.64; 0.82; 1, with 1% standard deviation (referenced as Fa45, Fa64, Fa82 and Fa100, respectively). All experiments were performed in the multi-anvil apparatus installed at NSLS beamline X17B2, to pressures up to about 7 GPa. Unit-cell volumes under hydrostatic conditions and differential stresses present in the samples were calculated using the method developed by Singh et al. (1998), and pressures measured using NaCl as a standard were then corrected for these stresses. Using a second-order Birch–Murnaghan equation of state, we obtained the isothermal bulk modulus of each composition: $K_{T0}^{\mathrm{Fa45}}=131.4\pm 2.6$ GPa, $K_{T0}^{\mathrm{Fa64}}=132.1\pm 3.1$ GPa, $K_{T0}^{\mathrm{Fa82}}=136.3\pm 1.7$ GPa and $K_{T0}^{\mathrm{Fa100}}=134.8\pm 1.4$ GPa. These values combined with data available in the literature show that the K_T0 of Fe-rich olivines increases very slowly with the Fe content, but possibly not in a simple linear trend.     

Relations entre production organique et apports terrigènes dans les sédiments fluviatiles holocènes : observations et conclusions hétérodoxes

Accumulation of organic matter in fens of fluvial valleys is often related to a low terrigenous matter delivery and to palaeoenvironmental conditions inducing low mechanical erosion. These assumptions come from the interpretation of contents in organic (MO) and mineral (MM) matters in sediments, expressed in percents, and then exactly anticorrelated. Calculation of mass accumulation rates of MO $(T_{{\mathrm{a}}_{\mathrm{MO}}})$ and MM $(T_{{\mathrm{a}}_{\mathrm{MM}}})$, expressed in g?m^?2?yr^?1, shows that $T_{{\mathrm{a}}_{\mathrm{MO}}}$ and $T_{{\mathrm{a}}_{\mathrm{MM}}}$ generally are not anticorrelated and that high values of $T_{{\mathrm{a}}_{\mathrm{MO}}}$ and $T_{{\mathrm{a}}_{\mathrm{MM}}}$ could appear simultaneously. That expression of MO and MM accumulation makes it possible to precise the climatic and human impact on sedimentation. To cite this article: J.-J. Macaire et al., C. R. Geoscience 337 (2005).     

Thermodynamic modeling of binary CH4–CO2 fluid inclusions

An equation of state (EOS) explicit in Helmholtz free energy has been improved to calculate the PVTx and vapor–liquid phase equilibrium properties of CH₄–CO₂ fluid mixture. This EOS, where four mixing parameters are used, is based on highly accurate EOSs recommended by NIST for pure components (CH₄ and CO₂) and contains a simple generalized departure function presented by Lemmon and Jacobsen (1999). Comparison with experimental data available indicates that the EOS can calculate both vapor–liquid phase equilibrium and volumetric properties of this binary fluid system with accuracy close to that of experimental data up to high temperature and pressure within full range of composition. The EOS of CH₄–CO₂ fluid, together with the updated Gibbs free energy model of solid CO₂ (dry ice), is applied to calculate the CH₄ content (x_CH4) and molar volume (V_m) of the CH₄–CO₂ fluid inclusion based on the assumption that the volume of an inclusion keeps constant during heating and cooling. $V_{\text{m}}-x_{{\text{CH}}_4}$ diagrams are presented, which describe phase transitions involving vapor, liquid and CO₂ solid phases of CH₄–CO₂ fluid inclusions. Isochores of CH₄–CO₂ inclusions at given $x_{{\text{CH}}_4}$ and V_m can be easily calculated from the improved EOS.