Investigation on the chemical structure of nonextractable residues of the fungicide cyprodinil in spring wheat using 13C-C1-phenyl-cyprodinil on 13C-depleted plants-an alternative approach to investigate nonextractable residues

13C-labelled cyprodinil was applied on 13C-depleted wheat plants with 27-fold field application rate. A control experiment applying same amounts of 14C-cyprodinil showed that main portions of the residues were detected in the cellulose (15% NER), hemicellulose (28.3% NER), and lignin fraction (23.3% NER). 16.7% were detected in water soluble polymers, 6% in both, pectin and protein fraction, and 4% in the starch containing fraction. Free cyprodinil was detectable by TLC in all fractions except lignin. A direct characterization of the residues in vivo by CP-MAS was not successful. Cell wall fractions were further analysed by liquid state NMR to determine the structure of the mobilized highly polymer/polar residues: Within lignin, where most of the residues were located at field application rate, neither intact cyprodinil nor its metabolites could not be detected. The 13C-label introduced was probably incorporated in the polymer as natural lignin monomers and thus are not considered as bound residues according to IUPAC definition.     

Use of 15N-depleted artificial compost in bound residue studies

Association of bound residues to soil humic matter may be accomplished by different binding mechanisms such as sequestration in hydrophobic interiors of the organic material or covalent linkage to the organic matter. The structures and chemical environments of compounds can be observed by NMR spectroscopy. We applied 15N-NMR spectroscopy to study the soil-bound residues of 15N-labeled simazine. As the 15N-isotope has a low sensitivity and natural abundance 15N-NMR experiments require long measurement times and often result in low signal-to-noise (S/N) ratios. Therefore, in addition to the use of 15N-labeled simazine, 15N-depleted compost was used to reduce the amount of background signal and enhance the sensitivity. The compost was produced from maize and wheat plants grown on sand with 15N-depleted NH4NO3 as sole nitrogen source. The plants were freeze-dried, ground and mixed with sand for composting. After a composting period of 224 days analysis of the compost revealed a 15N-content of 267 ppm as opposed to a natural abundance of 3650 ppm. Characterization of this artificial compost produced parameter values similar to those of a natural compost. The 13C-NMR-spectra of the humic and fulvic acids during different stages of maturity showed that there was a shift from single-bond functional groups to more complex double-bond and aromatic structures. Experiments with this compost showed an increased signal intensity. The improved sensitivity made it possible to obtain interpretable NMR signals in contrast to experiments with 15N-simazine on native soil where no signals were detectable. The data indicated that the bound residues of simazine are composed of metabolites resulting from N-dealkylation and triazine ring destruction. Silylation of the bound residues showed a very strong binding of the residues to the matrix as only a small fraction could be solubilized.     

Der VG?D 2005 im überblick

Ohne Zusammenfassung     

Application of ground-based Lidar for studies of the dynamics of ozone in a mountainous basin

A ground-based Differential Absorption Lidar was employed to study the dynamics of atmospheric O3 within the planetary boundary layer of a basin in the 'Fichtelgebirge' mountains, NE Bavaria. In particular, the night-time dynamics of O3 linked to the ground were investigated. The Lidar system measured vertical profiles of O3 up to 1 km above ground. For detailed analysis of the night-time dynamics of ozone, supplementary data from three ground-based stations (measuring mixing ratios of O3 and NO(x), as well as meteorological parameters) are essential. The Lidar results could be evaluated with these data from various altitudes above the basin floor. For the station with the largest (vertical) distance to the ground-based Lidar, the agreement was very good at all times. The Lidar method proved to be useful for examining the spatial distribution of O3. The observed night-time decrease of O3 at the bottom of the basin was due to deposition and to advection of air masses containing less O3 from the mountain slopes.     

A chemosorptive cylindrical denuder designed for personal exposure measurements of isocyanates-evaluation on generated aerosols of 4,4'-methylenediphenyl diisocyanate

A denuder/filter system constructed for solvent-free personal exposure measurements was evaluated for separation of vapour and particulate 4,4'-methylenediphenyl diisocyanate (4,4'-MDI) generated from heated PUR-foam. The two different phases were collected in the denuder and on the filter, respectively, by chemosorption on a polydimethylsiloxane (SE-30)-dibutylamine (DBA) stationary phase. Both repeatability and the total mass concentration of 4,4'-MDI were similar to that obtained from the reference method, in this case an impinger/filter system. The penetration of particles through the denuder at 300 ml min(-1) was nearly 100% in the particle size range 25 to 700 nm, which fits well with the Gormley-Kennedy equation. Denuder/filter sampling of the 4,4'-MDI aerosol at 500 ml min(-1) yielded a phase distribution that was in accordance with the results from the reference method. The method limit of detection was 6 ng m(-3) and 4 ng m(-3) for the denuder and filter, respectively, when using an air sampling flow rate of 300 ml min(-1) and a sampling period of 15 min. This is well below the Swedish occupational exposure limit (OEL) of 50 and 100 microg m(-3) for an 8-hour working day and a 5-min period, respectively.     

Surface solar ultraviolet radiation: A theoretical approach of the SUVR reaching the ground in Athens, Greece

Daily total ozone observations made during 1985–1993 by both the Total Ozone Mapping Spectrometer (TOMS) flown on the Satellite Nimbus-7 and the Dobson Spectrophotometer have been used in order to investigate the fluctuations of the daily broad-band and spectral solar ultraviolet radiation reaching the ground. This investigation has been performed by employing a recently developed parametric algorithm for the estimation of the spectral and broad-band solar ultraviolet radiation which takes the total ozone variations into consideration. Total ozone reductions during the summertime from 1985 to 1993 over Athens, Greece (37.6° N, 23.4° E), cause an increase in the ultraviolet irradiance which reaches the ground of 0.54 %, 0.98 %, 2.60 % and 0.79 % per decade for the months of July at 300 nm, 312 nm, 320 nm and UVB (280-320 nm), respectively.     

Remote monitoring of air pollutant emissions from point sources by a mobile lidar/sodar system

This paper describes remote monitoring of air pollutant emissions by a mobile lidar (light detection and ranging)/ sodar (sound detection and ranging) system. First, measurements are carried out in the flue gas plume of a public power plant. The investigations focus mainly on quantifying SO2 emissions, but the uncertainties of such measurements are also emphasized. Furthermore, an example providing valuable data sets for the development and validation of plume dispersion models is outlined with measurements of the dilution of SO2 along the plume axis. Series of repeated determinations of SO2 emissions show a large variation in the obtained flux values, with moderate margins of error. Incomplete recording of the plume within the individual lidar scans, induced by strong looping movements of the flue gas plume, predominantly causes the variations of flux values. Therefore, the highest flux values determined are considered to be the most exact. This is verified by a comparison of measured fluxes with in situ measurements made by the plant operators. The results further indicate that lidar measurements illustrate the location and dimension of aerosol plumes better than the location and dimension of the plumes of gaseous compounds. The wind direction affecting the plume at any moment can be determined faster by lidar than by sodar because the latter requires much longer time intervals of signal averaging. Measurements show higher concentrations of SO2 compared with results from a Gaussian plume model for periods of less than 5 min after dispersion. The findings emphasize the suitability of remote sensing for detecting emissions and for investigating the propagation and dilution of air pollutant plumes.     

Screening and Scenarios of Traffic Emissions at Trier,Germany

SCOPE AND BACKGROUND: In the course of the European Council Directive on permissible air pollutant limit values, valid starting from 2005 there is an urgent call for action, particularly for fine dust (PM10). Current investigations (Junk & Helbig 2003, Reuter & Baumüller 2003) show that the limit values in certain places in congested areas are exceeded. Only if it is possible to locate these Hot Spots purposeful measures to reduce the ambient air pollution can be conducted. For an efficient identification of these Hot Spots numerical computer models or establishing special measurements networks are too expensive. Using the statistical model STREET 5.0 (KTT 2003) a cost-effective screening of the air pollution situation caused by the traffic can be done. METHODS: STREET is based on the 3-dimensional micro-scale non-hydrostatic flow- and dispersion model MISCAM (Eichhorn 1989). The results of over 100.000 different calculations with MISCAM are stored in a Database and used to calculate the emissions with STREET. In collaboration with the city council of Trier more than 150 streets were investigated, mapped, and calculated. A special urban climate measuring network supplies the necessary meteorological input data about the wind field and precipitation events in the valley of the Moselle. Information about road width and road orientation as well as building density was derived from aerial photographs. Traffic censuses and mobile air pollutants measurements supplied the remaining input data. We calculated the mean annual air pollutant concentrations for NO2, CO, SO2, O3, benzene as well as PM10. RESULTS: A comparison of the model results with the values obtained from the stations of the central emission measuring network of Rhineland-Palatinate (ZIMEN, annual report 2002) shows very good agreements. The model was not only used to calculate the annual air pollutant but also for urban planning and management. The absolute level of the air pollutant is mainly dependent on the amount of traffic in the street canyons. Therefore four different case-scenarios with varying quantity of traffic were calculated and interpreted for each street. The results of the calculation show that on the basis of the mean values for both NO2 and benzene, it is not to be expected that the limits PERSPECTIVES: Furthermore the model can be used to find the maximum tolerable numbers of cars for a street without exceeding the air pollutant thresholds.     

Bioremediation of Chlorobenzene-Contaminated Groundwater on Granular Activated Carbon Barriers

During the past decade, various promising technologies have been developed for the decontamination of groundwater insitu which do not require long-term pumping or high energy consumption. One approach is to use funnel and gate technology. In the case described here, the combination of adsorption of contaminants on granular activated carbon (GAC) and its biodegradation is applied to considerably extend the operating time of the filling material in the barrier system. Monochlorobenzene (MCB), a recalcitrant groundwater contaminant under anaerobic conditions, undergoes high-capacity adsorption on GAC up to about 450 mg per gram. Aerobic enrichment cultures, obtained from a contaminated aquifer, were able to mineralize initially adsorbed MCB. In respirometer experiments the rate of carbon dioxide formation was dependent on the equilibrium concentration of MCB. The oxygen consumption of activated carbon by means of autoxidative reactions may delay aerobic biodegradation in GAC filters. The oxygen uptake of pristine activated carbon amounted to 5.6 mg per gram GAC in laboratory column experiments. When GAC was pre-loaded with MCB, autoxidation rates were considerably reduced. Hence, it is advisable not to stimulate the biodegradation of MCB by oxygen supply in GAC biobarriers until after an initial period of solely sorptive MCB removal from the groundwater flow.