An Improved Gas Chromatographic Method for the Determination of C6–C12 Petroleum Hydrocarbons in Soil Water

In this work, investigations dealing with the determination of hydrocarbons in contaminated soil water are presented. The hydrocarbons under investigation range from low to high volatility compounds. A GC‐FID method was developed that due to its efficiency, routine suitability, relative rapidity, and low cost is suitable for the analysis of complex chemical mixtures of highly volatile hydrocarbons (with boiling points between 69 and 190°C). The standard used was a gasoline mixture with boiling points ranging from 100 to 190°C. For this standard, no supplementary preparation is needed and it is suitable for the whole range of hydrocarbons under investigation. The determination of the hydrocarbon content of the samples was performed applying univariate and multivariate statistical analysis to the experimental data. In the characterization of a contamination with highly volatile hydrocarbons of soil water originating from different depth layers from the chemistry location Leuna (Sachsen‐Anhalt, Germany), the advantages of a multivariate method are demonstrated in exemplary manner.     

Modelling the biogeochemistry of a tidal flat ecosystem with EcoTiM

The ecological tidal model simulates the cycling of carbon, nitrogen, phosphate, and silicate and describes the tidal, diurnal, and annual dynamics of the back barrier area of the island Spiekeroog in the German Bight. The region is characterized by strong tidal currents and extensive tidal flats. It is strongly influenced by the conditions in the southern part of the German Bight. This model study investigates the dependence of the model behavior on the boundary conditions and the forcing. The effect of short- and long-term sea level rise on nutrient and plankton dynamics is analyzed. As the model is set up as semi-Lagrangian with only a coarse approximation of the hydrodynamics, the seasonal and intratidal variability in the biogeochemical cycling can only be reproduced qualitatively. By varying the boundary conditions, the intrinsic dynamics of the back barrier area can be separated from boundary condition effects. This study shows that any agreement between model results and field data cannot be expected without correct boundary conditions. The seasonal variability is of major importance, while higher-frequency variability only plays a minor role.     

Unusual exsolution phenomena in omphacite and partial replacement of phengite by phlogopite + kyanite in an eclogite from the Erzgebirge

In the Erzgebirge Crystalline Complex, eclogites occur in three different high pressure (HP) units (1, 2 and 3) recording contrasting pressure (P)–temperature (T) conditions. Eclogites from HP-unit 1 experienced peak metamorphic conditions in the coesite stability field at about 33 kbar/850 °C. Commonly, these eclogites from HP-unit 1 are all very similar, with an eclogitic peak assemblage of omphacite–garnet–coesite–K-feldspar, rarely accompanied by kyanite, and omphacites systematically deviating from a stoichiometric composition. In contrast, an eclogite recently found near Blumenau, is mineralogically and geochemically different from the typical eclogites of HP-unit 1. This unusual eclogite reveals the eclogitic equilibrium assemblage omphacite–garnet–coesite–phengite–phlogopite–kyanite, and yields metamorphic peak conditions of 870 °C and >29 kbar. There is clear textural evidence of the formation of phlogopite and kyanite under partial consumption of phengite and garnet. Moreover, the omphacite is stoichiometric and contains abundant exsolution lamellae, the thickest of which were identified as quartz by the electron microprobe. The finer lamellae were studied by transmission electron microscopy (TEM). Oligoclase was identified as an exsolution phase. Other lamellae proved to consist of K-white mica, also interpreted as exsolution. Prior to exsolution, the omphacite composition must have been cation-deficient, as that of the other, common HP-unit 1 eclogites. These non-stoichiometric compositions are ascribed to partial substitution by the Ca-Eskola pyroxene component, which calculates to an average of 8 mol% for omphacite in HP-unit 1 eclogites. According to experiments, this substitution becomes significant at P > 30 kbar. Exsolution of K-white mica may indicate hydroxyl defects in the original omphacite, also favoured by high pressure. Oligoclase and K-white mica exsolution from Ca-Eskola-rich clinopyroxene has not previously been reported. The omphacite has a disordered C2/c structure; and in just one case very small (a few tens of nanometres) antiphase domains, resulting from the C2/c to P2/n transformation, are present. These features may indicate a brief thermal history and rapid tectonic processes. Received: 4 January 1999 / Accepted: 20 April 2000     

Identifying causes of ground-penetrating radar reflections using time-domain reflectometry and sedimentological analyses

Ground-penetrating radar (GPR) is a geophysical technique widely used to study the shallow subsurface and identify various sediment features that reflect electromagnetic waves. However, little is known about the exact cause of GPR reflections because few studies have coupled wave theory to petrophysical data. In this study, a 100- and 200-MHz GPR survey was conducted on aeolian deposits in a quarry. Time-domain reflectometry (TDR) was used to obtain detailed information on the product of relative permittivity (ɛ_r) and relative magnetic permeability (μ_r), which mainly controls the GPR contrast parameter in the subsurface. Combining TDR data and lacquer peels from the quarry wall allowed the identification of various relationships between sediment characteristics and ɛ_rμ_r. Synthetic radar traces, constructed using the TDR logs and sedimentological data from the lacquer peels, were compared with the actual GPR sections. Numerous peaks in ɛ_rμ_r, which are superimposed on a baseline value of 4 for dry sand, are caused by potential GPR reflectors. These increases in ɛ_rμ_r coincide with the presence of either organic material, having a higher water content and relative permittivity than the surrounding sediment, or iron oxide bands, enhancing relative magnetic permeability and causing water to stagnate on top of them. Sedimentary structures, as reflected in textural change, only result in possible GPR reflections when the volumetric water content exceeds 0·055. The synthetic radar traces provide an improved insight into the behaviour of radar waves and show that GPR results may be ambiguous because of multiples and interference.     

Lippmann Diagrams: Theory and Application to Carbonate Systems

Since 1980 when F. Lippmann's seminal paper appeared, ourunderstanding of solubility equilibria involving ionic solidsolutions has been advanced by theoretical considerations as wellas careful experimental studies designed to determine excess Gibbsfunctions. A unified theory of solid-solution aqueous-solutionequilibria as well as the thermodynamic background of thephenomenon of ``stoichiometric saturation' are reviewed.It is shown that Lippmann diagrams effectively summarize thethermodynamic basis of solid-solute aqueous-solution equilibria ofsparingly soluble metal carbonate systems. Clearly, the predictivepower of these diagrams may be limited due to kineticrestrictions. Only when dissolution and precipitation areessentially reversible, favourable conditions to synthesizehomogeneous solid phases can be derived from studies of equilibria.     

Preserving the Ocean Circulation: Implications for Climate Policy

Climate modelers have recognized the possibility of abrupt climate changes caused by a reorganization of the North Atlantic's current pattern (technically known as a thermohaline circulation collapse). This circulation system now warms north-western Europe and transports carbon dioxide to the deep oceans. The posited collapse of this system could produce severe cooling in northwestern Europe, even when general global warming is in progress. In this paper we use a simple integrated assessment model to investigate the optimal policy response to this risk. Adding the constraint of avoiding a thermohaline circulation collapse would significantly reduce the allowable greenhouse gas emissions in the long run along an optimal path. Our analysis implies that relatively small damages associated with a collapse (less than 1% of gross world product) would justify a considerable reduction of future carbon dioxide emissions.     

Zircon M127 – A Homogeneous Reference Material for SIMS U–Pb Geochronology Combined with Hafnium,Oxygen and,Potentially, Lithium Isotope Analysis

In this article, we document a detailed analytical characterisation of zircon M127, a homogeneous 12.7 carat gemstone from Ratnapura, Sri Lanka. Zircon M127 has TIMS‐determined mean U–Pb radiogenic isotopic ratios of 0.084743 ± 0.000027 for ²⁰⁶Pb/²³⁸U and 0.67676 ± 0.00023 for ²⁰⁷Pb/²³⁵U (weighted means, 2s uncertainties). Its ²⁰⁶Pb/²³⁸U age of 524.36 ± 0.16 Ma (95% confidence uncertainty) is concordant within the uncertainties of decay constants. The δ¹⁸O value (determined by laser fluorination) is 8.26 ± 0.06‰ VSMOW (2s), and the mean ¹⁷⁶Hf/¹⁷⁷Hf ratio (determined by solution ICP‐MS) is 0.282396 ± 0.000004 (2s). The SIMS‐determined δ⁷Li value is ?0.6 ± 0.9‰ (2s), with a mean mass fraction of 1.0 ± 0.1 μg g^?1 Li (2s). Zircon M127 contains ~ 923 μg g^?1 U. The moderate degree of radiation damage corresponds well with the time‐integrated self‐irradiation dose of 1.82 × 10¹⁸ alpha events per gram. This observation, and the (U–Th)/He age of 426 ± 7 Ma (2s), which is typical of unheated Sri Lankan zircon, enable us to exclude any thermal treatment. Zircon M127 is proposed as a reference material for the determination of zircon U–Pb ages by means of SIMS in combination with hafnium and stable isotope (oxygen and potentially also lithium) determination.     

Exploring the impact of diagenesis on (isotope) geochemical and microstructural alteration features in biogenic aragonite

For the Quaternary and Neogene, aragonitic biogenic and abiogenic carbonates are frequently exploited as archives of their environment. Conversely, pre‐Neogene aragonite is often diagenetically altered and calcite archives are studied instead. Nevertheless, the exact sequence of diagenetic processes and products is difficult to disclose from naturally altered material. Here, experiments were performed to understand biogenic aragonite alteration processes and products. Shell subsamples of the bivalve Arctica islandica were exposed to hydrothermal alteration. Thermal boundary conditions were set at 100°C, 175°C and 200°C. These comparably high temperatures were chosen to shorten experimental durations. Subsamples were exposed to different ¹⁸O‐depleted fluids for durations between two and twenty weeks. Alteration was documented using X‐ray diffraction, cathodoluminescence, fluorescence and scanning electron microscopy, as well as conventional and clumped isotope analyses. Experiments performed at 100°C show redistribution and darkening of organic matter, but lack evidence for diagenetic alteration, except in Δ₄₇ which show the effects of annealing processes. At 175°C, valves undergo significant aragonite to calcite transformation and neomorphism. The δ¹⁸O signature supports transformation via dissolution and reprecipitation, but isotopic exchange is limited by fluid migration through the subsamples. Individual growth increments in these subsamples exhibit bright orange luminescence. At 200°C, valves are fully transformed to calcite and exhibit purple‐blue luminescence with orange bands. The δ¹⁸O and Δ₄₇ signatures reveal exchange with the aqueous fluid, whereas δ¹³C remains unaltered in all experiments, indicating a carbonate‐buffered system. Clumped isotope temperatures in high‐temperature experiments show compositions in broad agreement with the measured temperature. Experimentally induced alteration patterns are comparable with individual features present in Pleistocene shells. This study represents a significant step towards sequential analysis of diagenetic features in biogenic aragonites and sheds light on reaction times and threshold limits. The limitations of a study restricted to a single test organism are acknowledged and call for refined follow‐up experiments.