Gaschromatographische Bestimmung von polychlorierten Biphenylen in Wasser nach Headspace-Festphasenmikroextraktion

Gas-chromatographic Determination of Polychlorinated Biphenyls in Water after Headspace Solid-phase Microextraction Headspace-analytical techniques are usually applied to the determination of easily volatile substances in water, whereas semivolatiles are generally isolated by liquid-liquid or solid-phase extraction. In the present paper, a method is presented for isolating high boiling polychlorinated biphenyls (PCB) using headspace solid-phase microextraction at elevated temperature. In spite of their low vapor pressure, the analytes are adsorbed very efficiently on a poly-dimethylsiloxane-coated fiber. Thus, in combination with GC/ECD, a very simple and sensitive solventless determination of PCB is accomplished. Using the simplest possible standard conditions, limits of determination in the lowest nanogram-per-liter range are achieved. Further increased sensitivity down to the ppq (parts per quadrillion) range is possible by stirring and increasing the sample volume and adsorption time. Moderate matrix effects have been observed in some surface and groundwaters.     

Toxic Cyanobacteria in Greek Freshwaters, 1987—2000: Occurrence,Toxicity, and Impacts in the Mediterranean Region

In a survey in Greece from 1987 to 2000 hepatotoxic cyanobacterial blooms were observed in 9 out of 33 freshwaters. Microcystins (MCYSTs) were detected by HPLC in 7 of these lakes, and the total MCYST concentration per scum dry weight ranged from 50.3 to 1638 ± 464 μg g^—1. Cyanobacterial genera (Microcystis, Anabaena, Anabaenopsis, Aphanizomenon, Cylindrospermopsis) with known toxin producing taxa were present in 31 freshwaters. From our data and a review of the literature, it would appear that Mediterranean countries are more likely 1) to have toxic cyanobacterial blooms consisting of Microcystis spp. and 2) to have higher intracellular MCYST concentrations. A case study in Lake Kastoria is used to highlight seasonal patterns of cyanobacterial and MCYST‐LR occurrence and to assess cyanotoxin risk. Cyanobacterial biovolume was high (> 11 μL L^—1) throughout the year and was in excess of Guidance Level 2 (10 μL L^—1) proposed by WHO for recreational waters and Alert Level 2 for drinking water. Further, surface water samples from April to November exceeded Guidance Level 3, with the potential for acute cyanobacterial poisoning. Intracellular MCYST‐LR concentrations (max 3186 μg L^—1) exceeded the WHO guideline for drinking water (1 μg L^—1) from September to November with a high risk of adverse health effects. Preliminary evidence indicates that in 3 lakes microcystins are accumulated in some aquatic organisms. Generally, a high risk level can be deduced from the data for the Mediterranean region.     

Determining the maximum degree of harmonic coefficients in geopotential models by Monte Carlo methods

Random errors for the harmonic coefficients of a geopotential model are generated from the matrix of normal equations by a parallel computer applying the Gibbs sampler. This leads to random values for the harmonic coefficients. They are transformed by nonlinear, quadratic transformations to random values for the square roots of degree variances, of mean squares of geoid undulations and gravity anomalies. The expected values of these quantities are not equal to the values of these quantities computed by the estimated harmonic coefficients, due to correlations and errors in the estimation. By hypothesis tests estimated harmonic coefficients distorted by correlations and errors are detected. Applying the tests to the geopotential model ITG-CHAMP01 of the Institute of Theoretical Geodesy in Bonn it is concluded that above the degree 62 the harmonic coefficients cannot add any information to the geopotential model.     

Interpretation of gamma-ray logs: The distribution of uranium in carbonate platform

High gamma-radioactivity in carbonates is usually ascribed to uranium of detrital minerals and organic matter, and to thorium and potassium of clays. The present study based on Urgonian marls and marly limestones (France) shows that some of the most radioactive values correspond instead to some ‘pure’ limestones. These peaks are generally associated with a sequence boundary or a maximum flooding surface. Low-level γ-spectrometry and ICP–MS analyses show that although high radioactivities are mostly associated with uranium, there is no obvious correlation between uranium enrichment and lithology. Also, correlation between high radioactivity and argillaceous beds might not be systematic. To cite this article: M.C. Raddadi et al., C. R. Geoscience 337 (2005).     

Molecular formulae of marine and terrigenous dissolved organic matter detected by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

The chemical structure of refractory marine dissolved organic matter (DOM) is still largely unknown. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR-MS) was used to resolve the complex mixtures of DOM and provide valuable information on elemental compositions on a molecular scale. We characterized and compared DOM from two sharply contrasting aquatic environments, algal-derived DOM from the Weddell Sea (Antarctica) and terrigenous DOM from pore water of a tropical mangrove area in northern Brazil. Several thousand molecular formulas in the mass range of 300-600 Da were identified and reproduced in element ratio plots. On the basis of molecular elemental composition and double-bond equivalents (DBE) we calculated an average composition for marine DOM. O/C ratios in the marine samples were lower (0.36 ± 0.01) than in the mangrove pore-water sample (0.42). A small proportion of chemical formulas with higher molecular mass in the marine samples were characterized by very low O/C and H/C ratios probably reflecting amphiphilic properties. The average number of unsaturations in the marine samples was surprisingly high (DBE = 9.9; mangrove pore water: DBE = 9.4) most likely due to a significant contribution of carbonyl carbon. There was no significant difference in elemental composition between surface and deep-water DOM in the Weddell Sea. Although there were some molecules with unique marine elemental composition, there was a conspicuous degree of similarity between the terrigenous and algal-derived end members. Approximately one third of the molecular formulas were present in all marine as well as in the mangrove samples. We infer that different forms of microbial degradation ultimately lead to similar structural features that are intrinsically refractory, independent of the source of the organic matter and the environmental conditions where degradation took place.     

Stabilization of Atmospheric Concentrations of Greenhouse Gases

Given the present commitment of the developed countries according to the Kyoto Protocol, most published scenarios demonstrate that global greenhouse gases concentrations would not be stabilized at any level. In order to stabilize these concentrations, a deeper global involvement is needed. Taking Israel as an example of a `recently-developed' country, we assess the role that such countries could play by assuming voluntary commitments in strengthening global involvement. This case as a model may encourage a global scheme for curbing carbon emissions, in which the more developed countries assume a stronger role and the less developed countries participate according to the principle of common but differentiated responsibility. The scheme builds on the inverse relation that exists between the per capita gross domestic product and the rate of increase of emissions due to economic growth. According to this theoretical scheme, the voluntary commitments assumed by the `recently-developed' countries encourage the more developed countries to deepen their involvement by assuming more stringent reductions of emissions at home and transferring technological and financial means to the less developed countries. The proposed scheme would enable non-Annex I countries, both `recently-developed' countries and less developed countries, to participate much earlier in the net mitigation of greenhouse gases.     

Assessing the reliability of probabilistic flood inundation model predictions

An ability to quantify the reliability of probabilistic flood inundation predictions is a requirement not only for guiding model development but also for their successful application. Probabilistic flood inundation predictions are usually produced by choosing a method of weighting the model parameter space, but previous study suggests that this choice leads to clear differences in inundation probabilities. This study aims to address the evaluation of the reliability of these probabilistic predictions. However, a lack of an adequate number of observations of flood inundation for a catchment limits the application of conventional methods of evaluating predictive reliability. Consequently, attempts have been made to assess the reliability of probabilistic predictions using multiple observations from a single flood event. Here, a LISFLOOD‐FP hydraulic model of an extreme (>1 in 1000 years) flood event in Cockermouth, UK, is constructed and calibrated using multiple performance measures from both peak flood wrack mark data and aerial photography captured post‐peak. These measures are used in weighting the parameter space to produce multiple probabilistic predictions for the event. Two methods of assessing the reliability of these probabilistic predictions using limited observations are utilized; an existing method assessing the binary pattern of flooding, and a method developed in this paper to assess predictions of water surface elevation. This study finds that the water surface elevation method has both a better diagnostic and discriminatory ability, but this result is likely to be sensitive to the unknown uncertainties in the upstream boundary condition. Copyright © 2015 John Wiley & Sons, Ltd.