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.     

Biomonitoring zur wirkungsbezogenen Ermittlung der Schadstoffbelastung in terrestrischen Ökosystemen

Biomonitoring programmes provide relevant information, which may supplement ambient air pollution monitoring or modelling around emission sources. As a prerequisite, assessment scales for biomonitoring data have to be derived based on an objective evaluation of available data, as well as on a scheme of presentation, which is suggestive and easily understandable even for laymen. Based on an evaluation of numerous monitoring programmes, assessment scales for biomonitoring results are derived for plant biomonitoring, which also serve as a basis for the graphical presentation of monitoring results. This study is focussed on bioindicator plants like mosses (passive biomonitoring) and exposed lichens (active biomonitoring), in which 14 metal elements are investigated. As an example, data from a local biomonitoring network around a cement plant were used to demonstrate the use of the assessment scales derived and the presentation scheme developed. Data sets from about 15 moss and 24 lichen biomonitoring programmes, comprising more than 1000 specimens, were sorted by their pollutant characteristics in order to form the database. Data on the metal contents of species demonstrating similar values with respect to growth characteristics and habit, and representing background or low pollution levels, are aggregated and their statistical distributions are evaluated. Spacing of the assessment scales and their colour designations are derived from the 50-, 75-, 90- and 95-percentile values. Graphical presentation allows a comparison of the absolute values of metal contents and a relative association of measured values. Exemplary results from moss and lichen monitoring around a cement plant are generally below or slightly above the median values at background and low-pollution sites. Metal contents are higher in lichens compared to mosses for 7 elements (Cd, Cu, Hg, Pb, Sb, Sn, Zn), and are lower in lichens only for thallium. The assessment scheme presented is mainly aimed at the practitioner in the field of biomonitoring in order to provide a reliable and sound scale of assessment by comparison on an absolute scale rather than presenting the basis of ecological risk assessment. Differences in metal content of co-located samples of various moss species and possible correction procedures are briefly discussed- as well as the consequences of pooling monitoring data across various moss species for the quality of assessment scales. Further evaluations shall focus on species-specific rather than on pooled databases and will investigate the consequences of the use of correction factors when extrapolating metal data from one monitoring species to another.