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.     

Mercury accumulation in sediment and fish from rivers affected by alluvial gold mining in the Brazilian Madeira River basin,Amazon

The degree and distribution of mercury (Hg) accumulation in sediment and fish from a tributary affected by alluvial small-scale gold mining in the Madeira River/Amazon is studied, in relation to a reference site. The results obtained so far agree well with previous studies and confirm that a tremendous contamination of main food web compartments occurs in these highly exposed, but vulnerable tropical waters. An essential part of the released metallic Hg may still exist as macroscopic liquid Hg drops in the sediment. Both global (0.4 mg/kg of Hg) and local (0.1 mg/kg of Hg) background sediment values as well as safety levels for fish (0.5 mg/kg of Hg) are considerably exceeded by a factor of up to 25, 100, and 4, respectively, and give rise to serious concern, not least with regard to the formation of the very toxic monomethyl-Hg. It is further discussed that atmospheric transport and deposition of Hg in water reservoirs built for hydroelectric power generation may act as critical pathways for longterm Hg accumulation, even in unexposed riverine systems.