Lateglacial palaeoenvironments and palaeoclimates from Conty and Houdancourt, northern France, reconstructed from Beetle remains

Two Lateglacial insect sequences are described (a) from Conty, in the Selle valley and (b) from Houdancourt in the Oise valley, both in northern France. These investigations are part of a multidisciplinary investigation involving archaeology, sedimentology, geomorphology, geochronology and palaeontology (pollen, macroscopic plant remains, vertebrates, molluscs and insect fossils). The sequences of insect assemblages date from the latter part of the Bølling to the end of the Allerød periods. Environmental analysis of these faunas shows that rivers with riffles and pools meandered across flood plains. The river was extensively fringed with reedy vegetation. The only trees growing close to the river were of Salix and/or Populus. All the insect assemblages indicate that the thermal climates during the Bølling and Allerød periods were similar to one another and during both periods were very nearly as warm as that of the present day. No insect fossils were recovered from the sediments attributed to the Older Dryas interval though other evidence from these sites suggests that this event was decidedly colder than those immediately preceding and succeeding it. Comparisons are made between Lateglacial climatic patterns in northern France with those elsewhere in Europe.     

The isotopic effects of electron transfer: An explanation for Fe isotope fractionation in nature

Isotope fractionation of electroplated Fe was measured as a function of applied electrochemical potential. As plating voltage was varied from −0.9 V to 2.0 V, the isotopic signature of the electroplated iron became depleted in heavy Fe, with δ⁵⁶Fe values (relative to IRMM-14) ranging from −0.18(±0.02) to −2.290(±0.006) ‰, and corresponding δ⁵⁷Fe values of −0.247(±0.014) and −3.354(±0.019) ‰. This study demonstrates that there is a voltage-dependent isotope fractionation associated with the reduction of iron. We show that Marcus’s theory for the kinetics of electron transfer can be extended to include the isotope effects of electron transfer, and that the extended theory accounts for the voltage dependence of Fe isotope fractionation. The magnitude of the electrochemically-induced fractionation is similar to that of Fe reduction by certain bacteria, suggesting that similar electrochemical processes may be responsible for biogeochemical Fe isotope effects. Charge transfer is a fundamental physicochemical process involving Fe as well as other transition metals with multiple isotopes. Partitioning of isotopes among elements with varying redox states holds promise as a tool in a wide range of the Earth and environmental sciences, biology, and industry.     

Potentiometric titrations of Bacillus subtilis cells to low pH and a comparison of modeling approaches

To provide constraints on the speciation of bacterial surface functional groups, we have conducted potentiometric titrations using the gram-positive aerobic species Bacillus subtilis, covering the pH range 2.1 to 9.8. Titration experiments were conducted using an auto-titrator assembly, with the bacteria suspended in fixed ionic strength (0.01 to 0.3 M) NaClO₄ solutions. We observed significant adsorption of protons over the entire pH range of this study, including to the lowest pH values examined, indicating that proton saturation of the cell wall did not occur under any of the conditions of the experiments. Ionic strength, over the range studied here, did not have a significant effect on the observed buffering behavior relative to experimental uncertainty. Electrophoretic mobility measurements indicate that the cell wall is negatively charged, even under the lowest pH conditions studied. These experimental results necessitate a definition of the zero proton condition such that the total proton concentration at the pH of suspension is offset to account for the negative bacterial surface charge that tends towards neutrality at pH <2.The buffering intensity of the bacterial suspensions reveals a wide spread of apparent pKa values. This spread was modeled using three significantly different approaches: a Non-Electrostatic Model, a Constant Capacitance Model, and a Langmuir-Freundlich Model. The approaches differ in the manner in which they treat the surface electric field effects, and in whether they treat the proton-active sites as discrete functional groups or as continuous distributions of related sites. Each type of model tested, however, provides an excellent fit to the experimental data, indicating that titration data alone are insufficient for characterizing the molecular-scale reactions that occur on the bacterial surface. Spectroscopic data on the molecular-scale properties of the bacterial surface are required to differentiate between the underlying mechanisms of proton adsorption inherent in these models. The applicability and underlying conceptual foundation of each model is discussed in the context of our current knowledge of the structure of bacterial cell walls.     

Decoupling of arsenic and iron release from ferrihydrite suspension under reducing conditions: a biogeochemical model

High levels of arsenic in groundwater and drinking water are a major health problem. Although the processes controlling the release of As are still not well known, the reductive dissolution of As-rich Fe oxyhydroxides has so far been a favorite hypothesis. Decoupling between arsenic and iron redox transformations has been experimentally demonstrated, but not quantitatively interpreted. Here, we report on incubation batch experiments run with As(V) sorbed on, or co-precipitated with, 2-line ferrihydrite. The biotic and abiotic processes of As release were investigated by using wet chemistry, X-ray diffraction, X-ray absorption and genomic techniques. The incubation experiments were carried out with a phosphate-rich growth medium and a community of Fe(III)-reducing bacteria under strict anoxic conditions for two months. During the first month, the release of Fe(II) in the aqueous phase amounted to only 3% to 10% of the total initial solid Fe concentration, whilst the total aqueous As remained almost constant after an initial exchange with phosphate ions. During the second month, the aqueous Fe(II) concentration remained constant, or even decreased, whereas the total quantity of As released to the solution accounted for 14% to 45% of the total initial solid As concentration. At the end of the incubation, the aqueous-phase arsenic was present predominately as As(III) whilst X-ray absorption spectroscopy indicated that more than 70% of the solid-phase arsenic was present as As(V). X-ray diffraction revealed vivianite Fe(II)₃(PO₄)₂.8H₂O in some of the experiments. A biogeochemical model was then developed to simulate these aqueous- and solid-phase results. The two main conclusions drawn from the model are that (1) As(V) is not reduced during the first incubation month with high Eh values, but rather re-adsorbed onto the ferrihydrite surface, and this state remains until arsenic reduction is energetically more favorable than iron reduction, and (2) the release of As during the second month is due to its reduction to the more weakly adsorbed As(III) which cannot compete against carbonate ions for sorption onto ferrihydrite. The model was also successfully applied to recent experimental results on the release of arsenic from Bengal delta sediments.     

Environmental controls on clay mineralogy of an Early Jurassic mudrock (Blue Lias Formation,southern England)

We present a dataset including clay mineralogy, gamma-ray spectrometry, organic matter content and magnetic susceptibility of the Hettangian to lowest Sinemurian successions of Dorset and Somerset, southern UK (Blue Lias Formation, Bristol Channel and Wessex basins). In both areas, the clay assemblages comprise predominantly detrital illite, kaolinite and illite/smectite mixed layers. Clays probably originated from the erosion of the Hercynian massifs, the relative proportions of kaolinite and illite being modulated by arid-humid climatic fluctuations. The organic matter (OM) content (types II to IV) ranges up to 12% in both areas. A clear stratigraphical trend in clay mineral assemblages is apparent in Somerset, whereas in Dorset sharp contrasts between adjacent horizons and a greater dilution by carbonate mask the long-term evolution. Correlations between both areas based on similar vertical trends in clay mineral abundance support the suggestion of a hiatus within the angulata Zone of the Dorset succession. As expected, the kaolinite/illite ratio correlates with the Th/K ratio deduced from gamma-ray spectrometry. However, significant departures from the correlation occur in OM-rich intervals, suggesting that Th may be partly adsorbed on to OM particles. Surprisingly, high magnetic susceptibility correlates with abundant kaolinite, not with Fe-rich clays, indicating either that kaolinite is accompanied by a soil-inherited magnetisable phase (possibly iron oxide) or that illite-rich rocks are more strongly diluted by carbonate than are kaolinite-rich strata.     

A Compilation of Silicon,Rare Earth Element and Twenty‐One other Trace Element Concentrations in the Natural River Water Reference Material SLRS‐5 (NRC‐CNRC)

The natural river water certified reference material SLRS‐5 (NRC‐CNRC) was routinely analysed in this study for major and trace elements by ten French laboratories. Most of the measurements were made using ICP‐MS. Because no certified values are assigned by NRC‐CNRC for silicon and 35 trace element concentrations (rare earth elements, Ag, B, Bi, Cs, Ga, Ge, Li, Nb, P, Rb, Rh, Re, S, Sc, Sn, Th, Ti, Tl, W, Y and Zr), or for isotopic ratios, we provide a compilation of the concentrations and related uncertainties obtained by the participating laboratories. Strontium isotopic ratios are also given.     

Chromium speciation in oxide-type compounds: application to minerals,gems, aqueous solutions and silicate glasses

Cr K-edge XANES spectra were obtained for a variety of Cr-bearing model compounds containing Cr(II), Cr(III), Cr(IV), Cr(V) and Cr(VI), in which the Cr-site symmetry is D4h, Oh and Td. The centroid position of the pre-edge feature is a better indicator of the Cr valence than the edge position. In Cr-rich oxides, higher-energy transitions must be excluded in order to refine a robust valence for Cr. The pre-edge for chromates is not unique and varies as a function of the CrO₄ ^2? moiety distortion, which is often related to Cr-polymerization (monochromate vs. dichromate). Both the analogy with the Mn K-pre-edge information and ab initio FEFF calculations of the pre-edge feature for Cr(III) and Cr(VI) confirm the experimental trends. This methodology is applied to the Cr K-edge pre-edge feature collected in gems (emerald, spinel and ruby), the layered minerals fuchsite and kämmererite, two Cr-bearing aqueous solutions and a set of sodo-calcic silicate glasses used for bottling sparkling white wine. In emerald and fuchsite, the Cr-site is differently distorted than its ruby or spinel counterpart. In a Cr(III)-bearing aqueous solution and sodo-calcic glass, no evidence for Cr(III) with Td and C3v symmetry is detected. However, minor amounts of chromate moieties (most likely monomeric) are detected in a glass synthesized in air. Preliminary spectra for the wine bottle glass suggest that only trace amounts of chromates might possibly be present in these glasses.     

Quaternary geochemical evolution of the salars of Uyuni and Coipasa, Central Altiplano, Bolivia

The central trough of the Bolivian Altiplano is occupied by two wide salt crusts: the salar of Uyuni, which is probably the largest salt pan in the world (10,000 km²) and the salar of Coipasa (2,500 km²). Both crusts are essentially made of porous halite filled with an interstitial brine very rich in Li, K, Mg, B (up to 4.7 g/l Li, 4.3 g/l B, 30 g/l K and 75 g/l Mg). Lithium reserves are the highest known in the world, around 9 × 10⁶ tons. Potassium, magnesium and boron reserves in brines are also important (around 194 × 10⁶ tons K, 8 × 10⁶ tons B and 211 × 10⁶ tons Mg).

The crusts are the remnant of saline Lake Tauca (13,000–10,000 yr BP). Its salinity was estimated approximately at 80 g/l. Its paleochemistry was derived in two ways: (1) by dissolving the present amounts of all chemical components in the former lake volume, and (2) by simulating the evaporation of the major inflows to the basin. The resulting chemical compositions are quite different. The dissolution-derived one is 5 to 50 times less concentrated in Li, K, Mg, B than the evaporation-simulated ones. However all compositions present the same Na and Cl contents. This suggests either a removal of bittern salts or an enrichment of the former lake water in Na and Cl.

The most probable interpretation is that Lake Tauca redissolved a salt crust akin to that existing today. Several older lakes have been detected on the Altiplano. Nevertheless, such an explanation only pushes the problem back. It is likely that the anomaly was transferred from one lake to an other. Three hypotheses may be put forward: (1) bittern seepage through bottom sediments, (2) uptake of the missing components by minerals, and (3) leaching of ancient evaporites from the catchment area at the beginning of the lacustrine history of the basin. The excess halite could have been recycled from lake to lake. This latter process seems to be the most effective to explain the large excess of Na and Cl over the bittern solutes — Li, K, Mg and B. The occurrence of almost pure Na/1bCl saline springs flowing out from a gypsum diapir in the northern Altiplano gives substantial support to this hypothesis.     

Occurence of abundant diradicaloid moieties in the insoluble organic matter from the Orgueil and Murchison meteorites: a fingerprint of its extraterrestrial origin?

The highly aromatic structure of the macromolecular organic matter (OM) of the Murchison and Orgueil meteorites was recently shown to contain free organic radicals which are concentrated in micro-regions in contrast with terrestrial samples which always show an homogeneous distribution of radicals. An additional signature is revealed, in the present study, by the evolution of the radical concentration with temperature. Whereas in terrestrial samples, this concentration is independent of temperature (Curie magnetism), a significant increase is observed above 150 K in the two meteorites. Based on the electronic structure of organic radicals, calculated by Extended Hückel and Density Functional methods, this behavior was assigned to the occurrence of diradicaloid moieties hosted by aromatic structures of 10 to 15 rings and having a quinoidal structure. They represent 40 and 25% of the total radicals in Orgueil and Murchison, respectively. The search for the cosmochemical interpretation of this unique observation should open a new field of experimental investigations.     

Coupling statistical and dynamical methods for spatial downscaling of precipitation

The resolution of General Circulation Models (GCMs) is too coarse for climate change impact studies at the catchment or site-specific scales. To overcome this problem, both dynamical and statistical downscaling methods have been developed. Each downscaling method has its advantages and drawbacks, which have been described in great detail in the literature. This paper evaluates the improvement in statistical downscaling (SD) predictive power when using predictors from a Regional Climate Model (RCM) over a GCM for downscaling site-specific precipitation. Our approach uses mixed downscaling, combining both dynamic and statistical methods. Precipitation, a critical element of hydrology studies that is also much more difficult to downscale than temperature, is the only variable evaluated in this study. The SD method selected here uses a stepwise linear regression approach for precipitation quantity and occurrence (similar to the well-known Statistical Downscaling Model (SDSM) and called SDSM-like herein). In addition, a discriminant analysis (DA) was tested to generate precipitation occurrence, and a weather typing approach was used to derive statistical relationships based on weather types, and not only on a seasonal basis as is usually done. The existing data record was separated into a calibration and validation periods. To compare the relative efficiency of the SD approaches, relationships were derived at the same sites using the same predictors at a 300km scale (the National Center for Environmental Prediction (NCEP) reanalysis) and at a 45km scale with data from the limited-area Canadian Regional Climate Model (CRCM) driven by NCEP data at its boundaries. Predictably, using CRCM variables as predictors rather than NCEP data resulted in a much-improved explained variance for precipitation, although it was always less than 50?% overall. For precipitation occurrence, the SDSM-like model slightly overestimated the frequencies of wet and dry periods, while these were well-replicated by the DA-based model. Both the SDSM-like and DA-based models reproduced the percentage of wet days, but the wet and dry statuses for each day were poorly downscaled by both approaches. Overall, precipitation occurrence downscaled by the DA-based model was much better than that predicted by the SDSM-like model. Despite the added complexity, the weather typing approach was not better at downscaling precipitation than approaches without classification. Overall, despite significant improvements in precipitation occurrence prediction by the DA scheme, and even going to finer scales predictors, the SD approach tested here still explained less than 50?% of the total precipitation variance. While going to even smaller scale predictors (10–15?km) might improve results even more, such smaller scales would basically transform the direct outputs of climate models into impact models, thus negating the need for statistical downscaling approaches.