Anabolic, doping, and lifestyle drugs, and selected metabolites in wastewater—detection, quantification, and behaviour monitored by high-resolution MS and MS n before and after sewage treatment

Municipal wastewater has been examined for steroids, β₂-agonists, stimulants, diuretics, and phosphodiesterase type V inhibitors (PDE type V inhibitors), which are “dual-use-drugs” applied either as anabolic, doping, and lifestyle drugs or for treatment of diverse diseases. To identify their origin, fitness centre discharges under suspicion of being point sources and sewage-treatment plant feed and effluents were sampled and concentrations determined. Sensitive and selective methods for determination and quantification based on solid-phase extraction (SPE) followed by high-performance liquid chromatography–high resolution mass and tandem mass spectrometry (HPLC–(HR)MS and HPLC–MS–MS) were developed and established for analysis of these compounds in wastewater and to assess their effect on the environment. The methods developed enabled quantification at trace concentrations (limit of quantification (LOQ): 5 ng L⁻¹). Of the steroids and stimulants under investigation, testosterone, methyltestosterone, and boldenone or ephedrine, amphetamine, and MDMA (3,4-methylendioxy-N-methylamphetamine) were observed at up to 5 μg L⁻¹ (ephedrine). Of the β₂-agonists salbutamol only, and of the diuretics furosemide and hydrochlorothiazide were confirmed in the extracts. Quite high concentrations of the PDE type V inhibitors sildenafil, tadalafil, and vardenafil and their metabolites were confirmed in fitness centre discharges (sildenafil: 1,945 ng L⁻¹) whereas their concentrations in municipal wastewater did not exceed 35 ng L⁻¹. This study identified anabolic and doping drugs in wastewater for the first time. Results obtained from wastewater treatment plant effluents proved that these “dual-use-drugs”, with the exception of hydrochlorothiazide, were mostly eliminated.     

Synthesis and characterisation of the SrxBa1−xFeO3−y-system and the fluorinated phases SrxBa1−xFeO2F

Compounds in the system Sr_xBa_1?xFeO_3?y have been prepared under different partial pressures of oxygen. In this system, different perovskite-type structures are found depending highly on the values of x and y. Fluorination using polyvinylidenedifluoride (PVDF) gives oxyfluoride materials of composition Sr_xBa_1?xFeO₂F, which normally crystallize in the cubic perovskite structure. Rietveld refinement results provide information about the packing density for oxide and oxyfluoride samples and allow a general comparison between these two different types of materials. Furthermore, the determination of the average iron oxidation state also showed that the oxygen deficiency, y, depends significantly on the value of x and the structure determined by the Sr/Ba ratio.     

Development of Na+-sensitive membranes based on sputtered Na-Al-Si glasses

Na⁺-sensitive microdevices are of increasing interest for integration in microanalytical systems e.g. for biomedical applications or for industrial process control. In order to produce ultra thin Na⁺-sensitive layers with fixed and reproducible composition and, in particular, defined Na concentration by means of RF sputtering, an off-axis geometry of a magnetron with cylindrical target was chosen for minimizing back-sputtering effects from the already deposited material. With this inverted cylindrical magnetron (ICM) it was possible to obtain reproducible and controllable sodium aluminosilicate glass layers on semiconductor substrates. Several surface and thin layer analytical techniques were applied for characterization of the membranes and for stoichiometry control. Especially by the non-destructive nuclear reaction analysis method a constant Na profile throughout the glass layer and — together with AES depth profiles — the diffusion barrier effect of an Si₃N₄ interface layer could be verified. Electrochemical measurements proved Nernstian sensitivity down to 10^–4 M Na⁺ in solutions of pH 7, supporting sufficient stability and reproducibility of the sputtered Na⁺-sensitive layers.     

Perfluororganocadmium-verbindungen als sehr wirksame perfluoralkylierungs- und perfluorphenylierungsmittel zur darstellung von perfluororganozinn- und -blei-verbindungen [1]

Perfluoroorgano tin and lead compounds can be prepared in high yields from the reactions of (CH₃)₃SnOCOCF₃ and (CH₃)₃Pb(OCOCF₃) with perfluoroorgano cadmium complexes. (CH₃)₃SiOCOCF₃ reacts with (CF₃)₂Cd complexes — probably via the intermediate (CH₃)₃SiCF₃ and CF₂ elimination — to form (CH₃)₃SiF and CF₃CdOCOCF₃ complexes. While the reaction of (CF₃)₂Cd·D with (CH₃)₃SnONO₂ yields CF₃NO as the only volatile product, (R_f)₂Cd·D (R_f  C₂F₅, iC₃F₇) forms R_fCdONO₂·D and (CH₃)₃SnR_f. The preparations and properties of the partly new compounds as well as the n.m.r. spectra are described.