Chemisch-analytische Untersuchung von Arsenkampfstoffen und ihren Metaboliten

Zusammenfassung  Arsenkampfstoffe sind in der Umwelt persistent und kontaminieren bis heute Boden und Grundwasser. In diesem Beitrag werden die chemischen Reaktionen der Arsenkamptstoffe Diphenylarsinchlorid (CLARK I), Phenylarsindichlorid (PFIFFIKUS), Ethylarsindichlorid (DICK) sowie von Chlorvinylarsinverbindungen (LEWISITE) dargestellt. Die M?glichkeiten der chemisch-analytischen Erfassung dieser chemischen Kampfstoffe als Originalsubstanzen und als Thiol-Derivate werden pr?sentiert.      

A Simple Field Method to Determine Mercury Volatilization from Soils (3 pp)

Background Estimations of gaseous mercury volatilization from soils are often complex, stationary and expensive. Our objective was to develop a mobile and more simple, easy to handle and more cost-effective field method allowing rapid estimates of potential Hg emissions from soils. Methods. The study site is located in Germany, about 100 kilometers south-westerly of Berlin and influenced by the river Elbe and its tributary Saale river. The site is representative for a lot of other floodplain locations at the river Elbe and highly polluted with Hg and other heavy metals. For our study we developed a system consisting of a glass chamber gas, two gold traps, a battery operated pump and a gas meter. Adsorbed total gaseous mercury (TGM) in the gold traps was determined by use of atomic absorption spectrometry (AAS). Results and Discussion. In contrast to the common used flux chambers we designed a chamber without inlet and named it gas suck up chamber (GSC). TGM fluxes determined with the GSC showed a very close linear correlation (r = 0.993) between the TGM content in the gold traps and the corresponding pumped gas volume. The TGM adsorbed, increased proportional with increasing gas volume indicating homogenous concentrations of gaseous mercury in the soil air sucked. In contrast to the commonly used dynamic flux chamber with the aim of precisely measuring actual fluxes of Hg from a defined soil area, we focused on developing of a measurement system which will allow rapid estimates of potential Hg emissions of a site. Earlier research at the study site indicated a high potential for releasing volatile Hg from the soil to the atmosphere. Indeed, due to the high Hg content of the soil significant amounts of TGM could be detected and no shortage was reached. Conclusion. Our initial measurements are still too few in number neither to generalize the achieved results nor discuss controlling factors and processes. However, we are pleased to communicate that the developed GSC is well suited to become an effective sampling set up to rapidly estimate the magnitude of Hg volatilization from soils. Outlook. Further measurements at other polluted locations are necessary to verify the GSC method. In addition the use of a mercury analyzer instead of gold traps is planned for faster risk assessments.     

Passivsammler zur Wasseruntersuchung

Zusammenfassung  Durch r?umlich integrale Bestimmung der Schadstofffrachten [1] und zeitlich integrales Monitoring mit Schadstoff-Dosimetern [1] l?sst sich Topographie und Bewegung von Schadstofffahnen im Grundwasser bestimmen. Konventionelle Methoden der Entnahme und Untersuchung von Wasserproben sind ungeeignet zur Erfüllung dieser Anforderungen. Sorptionsaktive Passivsammler, die für entsprechende Untersuchungen in der Gasphase konzipiert sind, eignen sich nicht zur Aquiferuntersuchung. Die Passivsammler zur Untersuchung im ungest?rten Aquifer sind zentraler Bestandteil eines Systems von Probenahme- und Messsonden, das die Autoren für das Monitoring chemischer und hydraulischer Wasser-Parameter entwickelt haben. Mit den Passivsammlern lassen sich die relativen Schadstofffrachten in beliebig enger tiefenorientierter Anordnung der Messpunkte und auch zeitlich integriert zur Gewinnung von vertikalen relativen Schadstofffracht-Profilen ermitteln. Organische und anorganische relative Schadstofffrachten k?nnen damit bestimmt werden. Die gaiasafe-Passivsammler sind einfach handhabbar und lassen sich nach standardisierten chemischen Analysenmethoden auswerten. Damit erfüllen sie eine Reihe wesentlicher Anforderungen an das zielführende Monitoring von Schadstofffahnen. Die Passivsammler sind auch geeignet für die In-situ-Untersuchung von ruhigen und bewegten Gew?ssern auch in gro?er Tiefe z.B. Abw?sserkan?le, Kl?ranlagen, Flüsse und Meere und insbesondere zum Nachweis von Kontaminanten und Spurenstoffen in Wasserproben. Online First: 10. 01. 2001     

Exudation of UV-light absorbing natural products by seedlings ofNuphar lutea

Summary Seedlings ofNuphar lutea (L.) Sm. were raised from seeds and cultivated in a synthetic sterile nutrient solution under physiologically controlled and undisturbed conditions. The extracellular release of carbon compounds from the plants into the surrounding medium was examined by direct carbon estimation, by various specific chemical assays and by HPLC analysis. Direct carbon estimation was not sensitive enough to obtain reliable values; five of six specific chemical assays also failed. Only the Folin-Denis assay indicated there was a production of phenolic compounds, which followed a linear course that took up to six days of incubation. The phenolic compounds ranged between 0.2 and 1.3 µg/h g dry weight. Rp-HPLC with UV detection yielded a major fraction containing at least five highly polar compounds (not retainable on reversed phase), and a minor fraction of at least eight less polar (rp-retainable) compounds. Exudation followed a linear course for some days up to a distinct level of saturation in the surrounding medium. Cultures incubated in light or absolute darkness exhibit the same production rates; however, lower temperatures caused significant reduction in the production rate and on the pattern of exuded compounds as well. After withdrawing the exuded compounds by rinsing the cultures, a new production can be repeatedly induced many times until the potential of the system is seemingly exhausted. Nuphar seedlings procedures are introduced as a new macrophyte system suitable for studying the mechanism of extracellular secretion among aquatic macrophytes.     

Domino syntheses of bioactive tetronic and tetramic acids

Natural products containing tetronic acid or tetramic acid moieties continue to attract the interest of chemists, biologists, and physicians due to their challenging structures and to the wide range of biological activities they display. This review portrays the structural varieties of tetronic and tetramic acids and the spectrum of possible therapeutically relevant effects in man for exemplary derivatives. Their biosynthetic origin from α-amino and α-hydroxy acids is briefly discussed as is the relationship between their structures and their modes of interaction with biochemical effectors such as metal cations or enzymes. A short overview of laboratory syntheses of the heterocyclic core structures of tetramic and tetronic acids is provided with an emphasis on those emulating the biosynthesis. A synthesis from the α-amino or α-hydroxy esters and the cumulated phosphorus ylide Ph₃PCCO based upon a domino addition–intra-Wittig alkenation sequence is presented with applications to the preparation of the antibiotics reutericyclin and tenuazonic acid, the cytotoxic melophlin B, and the enzyme inhibitor RK-682. Procedural advantages of immobilizing either starting component by attaching it to a resin and its exploitation in the parallel synthesis of libraries of potential drug candidates are described. The basic domino reaction can even be extended by further C–C bond forming steps when starting from suitable α-hydroxy or α-amino allyl esters. Depending on the chosen reaction conditions, bioactive intermediates of formally three to seven step long cascades can be obtained. Among them, herbicidal 3-alkyltetronic acids and lactone endoperoxides with antiplasmodial activity exceeding that of the natural antimalarial lead artemisinin. Hence, this domino reaction gives access to diversely functionalized derivatives of tetronic and tetramic acids. As it can also be ported to solid phase, it is ideally suited for parallel and combinatorial processing. Future developments might include running such domino sequences in continuous mode in arrays of “labs on microchips”.     

Global environmental consequences of increased biodiesel consumption in Switzerland: consequential life cycle assessment

This study assesses the direct and indirect environmental impacts to be expected if Switzerland should replace one percent of its current diesel consumption with imports of A) soybean methyl ester (SME) from Brazil, or B) palm methyl ester (PME) from Malaysia. In order to take into account possible future consequences, what-if scenarios were developed and assessed by means of a consequential LCA. In contrast to attributional LCA, the consequential approach uses system enlargement to include the marginal products affected by a change of the physical flows in the central life cycle. This means that the LCA considers all inputs and outputs which are linked to biodiesel production and that the product system is subsequently expanded to include the marginal products affected. Both future systems are assessed in comparison with the environmental scores of the fossil equivalent to biodiesel, i.e. diesel low in sulphur. The environmental burdens are measured by means of greenhouse gas emissions (GHG), land occupation and various non-aggregated and aggregated environmental impact indicators.In sum, the environmental impacts of an increased SME consumption depend on the environmental scores of the marginal replacement products on the world market, rather than on local production factors. In other words, the marginal products assumed to be affected are most important for the results obtained, i.e. in particular the marginal vegetable oil, fodder cake and land areas. In this study it is SME production increased at the expense of the available soybean oil which shifts the impacts associated with soybean oil production to the production of the marginal vegetable oils on the world market. In this perspective, it is not relevant in which country biodiesel production takes place, but rather which vegetable oil is involved. With respect to PME, the most relevant determining factor for the environmental impacts is the land area affected by the increased cultivation of oil palms. Currently, this expansion displaces primarily peat land and rain forest. This causes GHG emissions which are much higher than the emissions of the fossil reference. All in all, both PME from Malaysia and SME from Brazil cause more environmental impact than allowed by the Swiss tax redemption on agro-biofuels (max. 60% GHG emissions and 125% UBP of the fossil reference).