Development of a robust technique for sampling volatile metal(loid)s in wetlands

The formation of volatile organic and inorganic metals and metalloids in aquatic environments is a known, but not very intensively investigated, process. Several techniques have been developed over the past 10 years to determine these trace components. These techniques are of limited use in wetland environments, where samples have to be taken from the soil-water interface, and require an immediate sample analysis due to thermodynamic instabilities of the volatile metal(loid)s. This paper presents an innovative sampling technique for total concentrations of volatile metal(loid)s in wetlands, based on an in situ gas-water separation via a porous PTFE membrane and stabilising the volatile metal(loid)s in a liquid sorbent (NaOCl solution). Samples may thus be collected even at remote sites, where longer storage times have to be accounted for. The sampling system was tested by means of a laboratory facility simulating the generation of arsine and dimethyl arsine under abiotic conditions as well as under field conditions. Results for sampling efficiency, reproducibility, and long-term storage are presented. Application of the sampling system in the field is shown.     

ICP-AES detection of silicon carbide impurities volatilized in a graphite furnace with the use of carbon tetrachloride vapour

The analytical capability of high-temperature halogenation with carbon tetrachloride vapour in a graphite furnace was investigated for silicon carbide powder with known chemical composition and particle size. Intensity vs heating time curves were determined for analytical lines of Al, B, Ba, Ca, Cr, Cu, Fe, Mg, Mn, Ti, V and Si constituents, volatilized with and without the presence of CCl₄ vapour in the furnace atmosphere. Igniting 10 mg SiC at 2100 °C for 60 s in chlorinating atmosphere, the evaporated fraction of most of the constituents was higher than 90% (for Al about 50%). The line intensity vs sample mass (4–26 mg) relationships were linear for all impurities studied, while the intensity of silicon line showed a relatively small change with the sample mass. BEC (background equivalent concentration) values for this solid sampling technique (10 mg loaded sample) were 2–20 fold lower than those calculated for the conventional solution sample introduction method.     

Ruthenium-catalysed carbenoid cyclopropanation reactions with diazo compounds

The transition-metal catalysed cyclopropanation of olefinic bonds using diazo compounds as a carbene source is among the best developed and most useful transformations available to the synthetic organic chemist. Nevertheless, the quest for new catalyst/ligand systems continues in order to further extend the scope of this method and to identify more economical catalytic systems. In this tutorial review, several different ruthenium complexes are presented which have recently emerged as suitable catalysts for carbenoid cyclopropanation. For the model reaction--cyclopropanation of styrene(s) with diazoacetates--and also for some intramolecular cyclopropanation reactions highly remarkable results in terms of catalyst efficiency, product yields, dia- and enantioselectivity have been reported.     

Diiod(methylthio)gallan. Darstellung und reaktivität

Different synthetic routes for the preparation of diiodo(methylthio)gallane are given. Some reactions of this compound with Lewis bases, such as O(CH₃)₂, S(CH₃)₂, S₂(CH₃)₂, N(CH₃)₃, P(CH₃)₃, and other compounds, such as CH₃I, CH₃OH, C₂H₅OH, C₂H₅SH, i-C₃H₇SH, and C₂H₅SeH are investigated. Spectra and some physical and chemical properties of the new compounds are reported. The structure of diiodo(methylthio)gallane is discussed in view of some interesting differences of this molecule in solution and in crystal form.     

Anordnung und Orientierung kationischer Tenside auf ebenen Silicatoberflächen

Zusammenfassung Die n-Alkylammoniumderivate der glimmerartigen Schichtsilicate können als Modellsubstanzen für die Anordnung kationischer Tenside an Festkörpergrenzflächen herangezogen werden. Im ersten Teil der Arbeit wird die Darstellung durch Kationenaustausch aus den natürlichen Schichtsilicaten beschrieben. Es wird ausführlich auf die Fehlerquellen hingewiesen, die reproduzierbare Messungen erschweren.

---

Summary The n-alkylammonium derivatives of mica-type layer silicates are suitable models for studies about the arrangement of cationic tensides at solid interfaces. Part I of the paper deals with the preparation of these compounds by a simple cation exchange reaction. Sources for errors in obtaining reproducible data are discussed in detail.

---

---

Mit 1 Abbildung in 3 Einzeldarstellungen und 3 Tabellen     

Elektronenmangelverbindungen des Galliums Zur Kenntnis von Ca3Ga5

Electron Deficient Compounds of Gallium: Crystal Structure of Ca₃Ga₅ The stoichiometry of the formerly described compound Ca₂Ga₃ is corrected to Ca₃Ga₅. This compound crystallizes in the orthorhombic system, space group Cmcm (No. 63) with the lattice constants see ?Inhaltsübersicht”?. In the structure there is a Ga framework for which on the basis of the Gillespie/Nyholm conception and by calculating the bond numbers according to Pauling a characteristic electron concentration can be derived.     

Evaluation of methods to measure differential 15N labeling of soil and root N pools for studies of root exudation

To study patterns of root exudation, the effectiveness of different techniques for in situ 15N labeling of Brassica napus, Centaurea jacea and Lolium perenne with ammonium nitrate was tested. Stem infiltration was found to effectively label plants with thicker stems, whereas, for grass species, cutting and immersing the leaf tips into 15N solution proved to be most effective. A microdiffusion technique to isolate ammonium, combined with conventional cation-exchange chromatography to separate nitrate from amino-N compounds thereafter, was found suitable for separation of the N fractions of plant and soil extracts for 15N determination. All three species were then cultivated in nutrient solution and labeled with 15NH4 15NO3 by stem feeding for 42 hours. Kinetics of 15N labeling of bulk roots and shoots as well as hot water extractable material were assessed, and up to 1.1 at% 15N excess (APE) was found in nutrient solutions. The main amino acids exuded by L. perenne were glycine, serine, alanine and aspartic acid. To assess the suitability of this set of methods to study root exudation in field settings, L. perenne was grown without fertiliser addition in pots containing low-nutrient soil. Plants were 15N labeled via tip immersion and 15N and N concentrations were analysed in shoots, roots and soils during a 48-h interval. Shoots reached 1.25 APE, roots and soil 0.10 and 0.005 APE, respectively. Between 4% (48 h) and 6% (24 h) of total plant 15N was exuded by roots into the soil. In roots amino acids comprised the largest proportion of the soluble 15N pool, whereas soil 15N levels were similar for amino acids and ammonium, exceeding those of nitrate. Mechanisms for the shift within N fractions from roots to soils are briefly discussed.