Simplification of a Sequential Extraction Scheme To Determine the Mobilisable Heavy Metal Pool in Soils

This investigation had the purpose of evaluating the reliability of a sequential extraction procedure according to Zeien and Brümmer (1989) which is performed routinely to analyse the distribution of heavy metals to different soil phases. Reliability was tested by two hypotheses. According to the first hypothesis an error propagation increased during a morefold extraction of heavy metals from a single soil sample to such an extend that it does not allow a statistical comparison of different analyses. This assumption was confirmed in an interlaboratory study of five participants applying the sequential extraction scheme on two different soils. The heavy metal amounts extracted by the different partners were of the same magnitude, but from the results no statistical correspondence at the 95% confidence level could be observed. The second hypothesis stated that also weak extraction agents were able to release metals from the more immobile soil fractions, especially if the amount of easily soluble metals was comparatively small. To answer this question the sequential extraction was modified by carrying out selected weak extraction steps several times. As expected the intensified extraction conditions caused a decrease of the element content within the more resistant phases. However, the additional release in the first four extraction steps of Pb, Mn, Fe, and Zn was only in the range of 5 to 10%. Furthermore, it was observed that a single EDTA extraction (step four within the sequential extraction scheme) was capable to extract the same amount of metals as the first four extraction steps of the original scheme at a variation of about 15%. From these results it was concluded that the EDTA step alone already represents a reliable pool of mobilisable metals. Thus it can be maintained that such a simple single EDTA extraction can be used to assess the environmental risk from heavy metal contaminated soils or to predict the potential heavy metal release of soil remediation processes.     

Carbon isotope characteristics of the diaromatic carotenoid, isorenieratene (intact and sulfide-bound) and a novel isomer in sediments

Messinian marls from evaporitic cycle IV of the Gessoso-solfifera formation (Italy) are known to contain in high abundance the diaromatic carotenoid isorenieratene of green sulfur bacterial (Chlorobiaceae) origin along with a second diaromatic carotenoid. The previous tentative assignment of the latter as a cis diastereomer of isorenieratene has now been confirmed; this indicates that double bond isomerization occurs during early diagenesis and provides further evidence for the pathway proposed previously to link isorenieratene to a number of aromatic isoprenoid hydrocarbon biomarkers. Stable carbon isotopic data confirm the Chlorobiaceae origin of the intact all-trans isorenieratene isomer and indicate that the isomerization is accompanied by little or no kinetic isotope effect. Comparison of the δ¹³C values of each of the isolated carotenoids (measured as isorenieratane after hydrogenation) with those of their sulfide-bound counterpart in the polar fraction of the extracts (also measured as isorenieratane) indicates that sulfurization resulted in little depletion in ¹³C.     

Timescales of interface-coupled dissolution-precipitation reactions on carbonates

In the Earth's upper crust, where aqueous fluids can circulate freely, most mineral transformations are controlled by the coupling between the dissolution of a mineral that releases chemical species into the fluid and precipitation of new minerals that contain some of the released species in their crystal structure, the coupled process being driven by a reduction of the total free-energy of the system. Such coupled dissolution-precipitation processes occur at the fluid-mineral interface where the chemical gradients are highest and heterogeneous nucleation can be promoted, therefore controlling the growth kinetics of the new minerals. Time-lapse nanoscale imaging using Atomic Force Microscopy (AFM) can monitor the whole coupled process under in situ conditions and allow identifying the time scales involved and the controlling parameters. We have performed a series of experiments on carbonate minerals (calcite, siderite, dolomite and magnesite) where dissolution of the carbonate and precipitation of a new mineral was imaged and followed through time. In the presence of various species in the reacting fluid (e. g. antimony, selenium, arsenic, phosphate), the calcium released during calcite dissolution binds with these species to form new minerals that sequester these hazardous species in the form of a stable solid phase. For siderite, the coupling involves the release of Fe²⁺ ions that subsequently become oxidized and then precipitate in the form of Fe^III oxyhydroxides. For dolomite and magnesite, dissolution in the presence of pure water (undersaturated with any possible phase) results in the immediate precipitation of hydrated Mg-carbonate phases. In all these systems, dissolution and precipitation are coupled and occur directly in a boundary layer at the carbonate surface. Scaling arguments demonstrate that the thickness of this boundary layer is controlled by the rate of carbonate dissolution, the equilibrium concentration of the precipitates and the kinetics of diffusion of species in a boundary layer. From these parameters a characteristic time scale and a characteristic length scale of the boundary layer can be derived. This boundary layer grows with time and never reaches a steady state thickness as long as dissolution of the carbonate is faster than precipitation of the new mineral. At ambient temperature, the surface reactions of these dissolving carbonates occur on time-scales of the order of seconds to minutes, indicating the rapid surface rearrangement of carbonates in the presence of aqueous fluids. As a consequence, many carbonate-fluid reactions in low temperature environments are controlled by local thermodynamic equilibria rather than by the global equilibrium in the whole system.     

An early Palaeozoic supra-subduction lithosphere in the Variscides: new evidence from the Maures massif

Petrographic and geochemical studies of peridotites and melagabbros from the Maures massif (SE France) provide new constraints on the Early Palaeozoic evolution of the continental lithosphere in Western Europe. Peridotites occur as lenses along a unit rooted in the main Variscan suture zone. They are dominantly spinel peridotites and minor garnet–spinel peridotites. Spinel peridotites represent both residual mantle and ultramafic cumulates. Mantle-related dunites and harzburgites display high temperature textures, with olivine (Mg#_0.90), orthopyroxene (Mg#_0.90) and spinel (TiO₂ < 0.2%; Cr#_0.64–0.83) compositions typical of fore-arc upper mantle. Ultramafic cumulates are dunite adcumulates, harzburgite heteradcumulates and mesocumulates, melagabbro heteradcumulates and amphibole peridotites, with olivine (Mg#_0.85–0.89), orthopyroxene (Mg#_0.86–0.89) and Cr-spinel (TiO₂ = 0.5–3.3%; Cr#_0.7–0.98) compositions typical of ultramafic cumulates. Cr-spinel compositions of both spinel peridotite types suggest their genesis in a supra-subduction zone lithosphere. Core to rim zoning in spinel is related to the incomplete influence of regional metamorphism and serpentinisation. The covariation of major and minor elements with Al₂O₃ for cumulates is consistent with igneous processes involving crystal accumulation. Both mantle and cumulate dunites and harzburgites have U-shaped REE patterns and extremely low trace element contents, similar to peridotites from modern fore-arc peridotites (South Atlantic) and from ophiolites related to supra-subduction zones (Semail, Cyclops, Pindos, Troodos). Melagabbros also have U-shaped REE patterns similar to xenoliths from the Philippine island arc, but also similar to intrusive ultramafic cumulates from the Semail nappe of Oman related to a proto-subduction setting. A wehrlite has a REE pattern similar to that of amphibole peridotites reflecting metasomatism of clinopyroxene-bearing peridotites due to subduction-related fluids. The Maures spinel peridotites and melagabbros are therefore interpreted as the lowermost parts of a crustal sequence and minor residual mantle of lithosphere generated in a supra-subduction zone during Early Palaeozoic time. Garnet–spinel peridotites are chemically close to melagabbros, but have recorded high pressure metamorphism before their retrogression similar to spinel peridotites into amphibolites to greenschists facies metamorphism. They indicate burial to mantle depths of the margin of the supra-subduction lithosphere during the Early Palaeozoic continental subduction. Both peridotite types were exhumed during the Upper Palaeozoic continental collision. Comparable observations from other Variscan-related peridotites, in particular of the Speik complex of the Autroalpine basement, and a common age for the subduction stage allow extension of these regional conclusions to a broad area sharing the Cambrian suture zone, extending from the Ossa-Morena to the Bohemian massif.     

Regional Nested Model Simulations of Present Day and 2 × CO2 Climate over the Central Plains of the U.S.

A nested regional climate model is used to generate a scenario of climate change over the MINK region (Missouri, Iowa, Nebraska, Kansas) due to doubling of carbon dioxide concentration (2 × CO₂) for use in agricultural impact assessment studies. Five-year long present day (control) and 2 × CO₂ simulations are completed at a horizontal grid point spacing of 50 km. Monthly and seasonal precipitation and surface air temperature over the MINK region are reproduced well by the model in the control run, except for an underestimation of both variables during the spring months. The performance of the nested model in the control run is greatly improved compared to a similar experiment performed with a previous version of the nested modeling system by Giorgi et al. (1994). The nested model generally improves the simulation of spatial precipitation patterns compared to the driving general circulation model (GCM), especially during the summer. Seasonal surface warming of 4 to 6 K and seasonal precipitation increases of 6 to 24% are simulated in 2 × CO₂ conditions. The control run temperature biases are smaller than the simulated changes in all seasons, while the precipitation biases are of the same order of magnitude as the simulated changes. Although the large scale patterns of change in the driving GCM and nested RegCM model are similar, significant differences between the models, and substantial spatial variability, occur within the MINK region.     

The dissolution rates of natural glasses as a function of their composition at pH 4 and 10.6, and temperatures from 25 to 74°C

Far-from-equilibrium dissolution rates of a suite of volcanic glasses that range from basaltic to rhyolitic in composition were measured in mixed flow reactors at pH 4 and 10.6, and temperatures from 25 to 74°C. Experiments performed on glasses of similar composition suggest that dissolution rates are more closely proportional to geometric surface areas than their BET surface areas. Measured geometric surface area normalized dissolution rates (r_+,geo) at 25°C were found to vary exponentially with the silica content of the glasses. For pH 4 solutions this relation is given by:

(A1)     

FICUS,a new in-situ probe for resistivity measurements in unconsolidated marine sediments

Physical properties of shallow sediments measured at a particular site can not easily be extrapolated over a given profile. The number of samples required to define sediment properties adequately can then become time-consuming and expensive. Laboratory and in-situ experimentations have shown that electrical probing provides a useful complementary technique to extrapolate results from cores. These experiments have pointed out the need for quantitative, easily-transportable and fast resistivity measurements combining high vertical resolution with azimuthal resolution and full coverage, in the shallow subsurface. A new prototype probe called FICUS (Formation Imaging and Coring for Unconsolidated Sediments) has been developed to bridge this gap. FICUS is designed to provide in-situ high resolution electrical resistivity images of the upper few meters of shallow unconsolidated sediments.Laboratory experiments have been completed to test the feasibility of this technique to provide resistivity images of unconsolidated sediments. Laboratory images agree with theoretical predictions from numerical modelling. The obtained cm-scale resolution could be used for petrophysical and sedimentary purposes. The probe may offer additional information about changes in porosity and pore morphology caused by climatic cycles, since electrical resistivity is known to be especially sensitive to these changes. The probe could also allow to detect and map organic pollutants in the future.