Radial distribution of lead and lead isotopes in stem wood of Norway spruce: A reliable archive of pollution trends in Central Europe

Annual growth rings of a common hardwood species, Picea abies L., were investigated as a potential archive of past atmospheric Pb pollution. Wide distribution of trees in terrestrial settings and straightforward chronology are two advantages of this potential geochemical archive, but several processes described in the literature may obscure the trends in past Pb deposition. These confounding factors include, e.g., radial post-depositional mobility of Pb in xylem, and ecosystem acidification leading to higher bioavailability of Pb. One- to five-year annual wood increments were analyzed for Pb concentrations and ²⁰⁶Pb/²⁰⁷Pb ratios at Jezeri (JEZ), Uhlirska (UHL) and Na Lizu (LIZ), three sites in the Czech Republic, differing in atmospheric Pb loads. Three to four trees per site were included in the study. Distinct Pb concentration maxima between 1960 and 1990 at the two heavily polluted sites (JEZ and UHL) coincided with historical Pb emissions known from inventories of industrial production. No Pb concentration maxima were found at one site, LIZ, situated in a national park 150 km from major pollution sources. Spruce tree rings from JEZ, located just 5 km from coal-burning power stations, contained a large proportion of coal-derived Pb (a high-²⁰⁶Pb/²⁰⁷Pb ratio of 1.19). A coal-related maximum in ²⁰⁶Pb/²⁰⁷Pb in JEZ tree rings was found using two different analytical techniques, laser-ablation multi-collector ICP MS, and single-collector sector-field ICP MS. In a three-isotope graph (²⁰⁶Pb/²⁰⁷Pb vs. ²⁰⁸Pb/²⁰⁷Pb), tree-ring data plotted into the field of ombrotrophic (i.e., rain-fed) peat bogs, suggesting negligible contribution of bedrock-derived Pb in the xylem. We concluded that none of the potential confounding factors played a major role at our sites. Annual growth rings of P. abies in Central Europe faithfully recorded historical changes in atmospheric Pb depositions.     

The Energy Balance Experiment EBEX-2000. Part I: overview and energy balance

An overview of the Energy Balance Experiment (EBEX-2000) is given. This experiment studied the ability of state-of-the-art measurements to close the surface energy balance over a surface (a vegetative canopy with large evapotranspiration) where closure has been difficult to obtain. A flood-irrigated cotton field over uniform terrain was used, though aerial imagery and direct flux measurements showed that the surface still was inhomogeneous. All major terms of the surface energy balance were measured at nine sites to characterize the spatial variability across the field. Included in these observations was an estimate of heat storage in the plant canopy. The resultant imbalance still was 10%, which exceeds the estimated measurement error. We speculate that horizontal advection in the layer between the canopy top and our flux measurement height may cause this imbalance, though our estimates of this term using our measurements resulted in values less than what would be required to balance the budget. The National Center for Atmospheric Research is supported by the National Science Foundation     

The Turbulent Lagrangian Time Scale in Forest Canopies Constrained by Fluxes,Concentrations and Source Distributions

One-dimensional Lagrangian dispersion models, frequently used to relate in-canopy source/sink distributions of energy, water and trace gases to vertical concentration profiles, require estimates of the standard deviation of the vertical wind speed, which can be measured, and the Lagrangian time scale, T _L , which cannot. In this work we use non-linear parameter estimation to determine the vertical profile of the Lagrangian time scale that simultaneously optimises agreement between modelled and measured vertical profiles of temperature, water vapour and carbon dioxide concentrations within a 40-m tall temperate Eucalyptus forest in south-eastern Australia. Modelled temperature and concentration profiles are generated using Lagrangian dispersion theory combined with source/sink distributions of sensible heat, water vapour and CO₂. These distributions are derived from a multilayer Soil-Vegetation-Atmospheric-Transfer model subject to multiple constraints: (1) daytime eddy flux measurements of sensible heat, latent heat, and CO₂ above the canopy, (2) in-canopy lidar measurements of leaf area density distribution, and (3) chamber measurements of CO₂ ground fluxes. The resulting estimate of Lagrangian time scale within the canopy under near-neutral conditions is about 1.7 times higher than previous estimates and decreases towards zero at the ground. It represents an advance over previous estimates of T _L , which are largely unconstrained by measurements.     

Influence of surface/groundwater interaction on pollution by pesticides in farmlands of the Fucino Plain,central Italy

This paper analyses flow and transport of pesticides from the unsaturated zone to groundwater so as to predict concentration of those contaminants in the Fucino Plain’s groundwater, by site investigations and numerical simulations. Pesticides were detected in surface water (peaks of 13 μg L⁻¹) and groundwater (peaks of 0.37 μg L⁻¹). Modelling tools made it possible to identify that pattern of precipitation, organic matter content, and root thickness are the key factors involved in vertical seepage of pesticides. Numerical simulations indicated that a significant fraction of contaminants is leached from the most surficial soil layers through runoff, while only a secondary fraction is mobilised towards groundwater. Likelihood of contaminating deep groundwater is fairly low, whereas surface waters show higher susceptibility. Results of the proposed conceptual hydrogeological model show that pesticides are more likely to be entrained by mixing of stream water with shallow groundwater in periods of high water exploitation from shallow wells.     

Effects of base catalysis on the product distribution from pyrolysis of woody biomass in the presence of water

Previous work has shown that woody biomass can generate oil-like products during hydrous pyrolysis. However, the yield of extractable organic matter is rather small, and the proportion of coke is high. In order to increase the oil yield and decrease the coke generation, experiments with added base catalysts have been made. NaOH was chosen as the catalyst. Experimental design is used to investigate the effects of variable experimental conditions during pyrolysis. The results are compared with similar experiments without a catalyst, and show a general decrease in coke formation and increase in the extractable organic matter with a dominance of polar compounds. The variable with the largest effect on yields is the amount of water, while pyrolysis temperature and the amount of starting material have minor effects.     

Nitrogen Mass Fraction and Stable Isotope Ratios for Fourteen Geological Reference Materials: Evaluating the Applicability of Elemental Analyser Versus Sealed Tube Combustion Methods

Thirteen commercially available silicate reference materials (RM) and one in‐house reference material, eleven of which have no previously published values, were analysed for nitrogen mass fraction and isotopic ratios with an Elemental Analyser (EA), and a Sealed Tube Combustion line, coupled to a continuous flow isotope ratio mass spectrometer (IRMS). These materials ranged from < 10 μg g^?1 to 1% m/m nitrogen mass fractions and δ¹⁵N of ?0.5 to +19.8‰. Existing nitrogen RM BHVO‐2, MS#5 and SGR‐1b were used to assess the accuracy of the data from the sealed tube combustion line, which was found to be in good agreement with existing published values. In contrast, the EA‐IRMS failed to fully liberate nitrogen from all silicate rocks and minerals (achieving a mean of 44 ± 10% nitrogen yield) resulting in kinetic fractionation of isotope values by ?1.4‰ on average. Therefore, sealed tube combustion is better suited for analyses of silicate‐bound nitrogen. The EA worked reliably for organic samples, but care should be taken when using the EA for silicate nitrogen research. Moving forward, it is recommended that BHVO‐2, Biotite‐Fe, FK‐N and UB‐N be used as quality control materials as they appear to be most reproducible in terms of nitrogen mass fraction (relative error < 10%, 1s), and isotopic composition (< 0.6‰, 1s).     

Die Kristallstruktur von Denningit, (Mn,Ca,Zn) Te2O5. Ein Beispiel für die Koordination um vierwertiges Tellur

Zusammenfassung Denningit, (Mn, Ca, Zn) Te₂O₅ ist tetragonal mit der Raumgruppe P 4₂/n bc und den Gitterkonstanten a=8,82, c=13,04; Z=8. Die Struktur wurde mit Patterson-, Fourier- und (F_o-F_c)-Projektionen parallel [100], [110] und [001] bestimmt und verfeinert. Abschließend konnte eine least-squares-Verfeinerung durchgeführt werden. Je zwei trigonale TeO₃-Pyramiden (Te–O=1,84–2,04 ) sind zu isolierten Te₂O₅-Gruppen verbunden. Mn, Ca und Zn in 8- und in [4+2]-Koordination bilden längs [001] Ketten, die durch Te₂O₅-Gruppen miteinander verknüpft sind.

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Summary Denningite, (Mn, Ca, Zn) Te₂O₅ is tetragonal with spacegroup P 4₂/n bc and unit-cell dimensions a=8,82, c=13,04; Z=8. The structure has been determined and refined by Patterson, Fourier and (F_o-F_c) projections along [100], [110] and [001]. Finally a least-squares refinement has been carried out. Pairs of trigonal TeO₃ pyramids (Te–O=1,84–2,04) are connected to isolated Te₂O₅ groups. Mn, Ca and Zn in 8 coordination and in [4+2] coordination form chains along [001] connected by Te₂O₅ groups.

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Mit 3 Textabbildungen

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Herrn Professor Dr.F. Machatschki zum 70. Geburtstag gewidmet