Diffusive sampling of methyl isocyanate using 4-nitro-7-piperazinobenzo-2-oxa-1,3-diazole (NBDPZ) as derivatizing agent

A diffusive sampling method for the determination of methyl isocyanate (MIC) in air is introduced. MIC is collected using a glass fiber filter impregnated with 4-nitro-7-piperazinobenzo-2-oxa-1,3-diazole (NBDPZ). The urea derivative formed is desorbed from the filter with acetonitrile and analyzed by means of high-performance liquid chromatography (HPLC) using fluorescence detection (FLD) with lambdaex = 471 nm and lambdaex = 540 nm. Additionally, a method was developed using tandem mass spectrometric (MS-MS) detection, which was performed as selected reaction monitoring (SRM) on the transition [MIC-NBDPZ + H]+ (m/z 307) to [NBDPZ + H]+ (m/z 250). The diffusive sampler was tested with MIC concentrations between 1 and 35 microg m(-3). The sampling periods varied from 15 min to 8 h, and the relative humidity (RH) was set from 20% up to 80%. The sampling rate for all 15 min experiments was determined to be 15.0 mL min(-1) (using HPLC-FLD) with a relative standard deviation of 9.9% for 56 experiments. At 80% RH, only 15 min sampling gave acceptable results. Further experiments revealed that humidity did not affect the MIC derivative but the reagent on the filter prior to and during sampling. The sampling rate for all experiments (including long term sampling) performed at 20% RH was found to be 15.0 mL min(-1) with a relative standard deviation of 6.3% (N = 42). The limit of quantification was 3 microg m(-3) (LC-MS-MS: 1.3 microg m(-3)) for 15 min sampling periods and 0.2 microg m(-3) (LC-MS-MS: 0.15 microg m(-3)) for 8 h sampling runs applying fluorescence detection.     

Control of ammonia toxicity to Hyalella azteca by sodium, potassium and pH

The toxicity of ammonia to Hyalella azteca at constant pH in artificial media was controlled by sodium and potassium, and not by calcium, magnesium, or anions. Small increases in the LC50 for total ammonia (from 0.15 to 0.5 mM) occurred as sodium was increased from 0.1 to 1 mM and above, but major increases in the LC50 (to over 10 mM total ammonia) required the addition of potassium. Potassium was, however, more effective at reducing ammonia toxicity at high (1 mM) sodium than at low (0.1 mM) sodium. Ammonia toxicity was independent of pH at low sodium and potassium concentrations, when ammonia toxicity appeared to be associated primarily with aqueous ammonium ion concentrations. At high sodium and potassium concentrations, the toxicity of ammonia was reduced to the point where un-ionized ammonia concentrations also affected toxicity, and the LC50 became pH dependent. A mathematical model was produced for predicting ammonia toxicity from sodium and potassium concentrations and pH.     

New biodegradable polyester-copolymers from commodity chemicals with favorable use properties

Copolyesters composed of aliphatic and aromatic compounds were synthesized by the polycondensation of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, sebacic acid, adipic acid, and terephthalic acid. By applying an appropriate ratio of aliphatic to aromatic acids, the synthesized materials proved to be biodegradable, as was verified by several degradation test methods such as aqueous polymer suspension inoculated by a soil eluate (Sturm test), a soil burial test (at ambient temperature), and a composting simulation test at 60°C. The degradability of the polyester-copolymers (measured as weight loss) was investigated with respect to the aliphatic monomer components and the fraction of terephthalic acid. Excellent biodegradability was observed even for copolymers with a content of terephthalic acid up to 56 mol% (of the acid fraction) and melting points in the range up to 140°C. Degradation by chemical hydrolysis of the polyesters was determined independently and was found to facilitate microbial attack significantly only at higher temperatures. The findings demonstrate that biodegradable polymers with advantageous usage properties can easily be manufactured by conventional techniques from commodity chemicals (adipic acid, terephthalic acid, and ethylene glycol or 1,4-butanediol).Dedicated to Prof. J. Klein's 60th birthday.