Effect of radial directional dependences and rainwater influence on CVOC concentrations in tree core and birch sap samples taken for phytoscreening using HS-SPME-GC/MS.

Phytoscreening for chlorinated volatile organic compounds (CVOC) in tree core samples is influenced by many factors. For instance, greater fluctuations are observed for CVOC concentrations in samples taken around the trunk at a fixed height compared to samples taken directly next to each other. To avoid false negatives and inaccurate interpretation of the results, we investigated this radial directional dependence as well as the influence of rainwater on measured concentrations. CVOC analysis was performed by gas chromatography/mass spectrometry (GC/MS) following Solid-Phase-Microextraction (SPME). Phytoscreening was successfully carried out at three sites using this method. In addition, sap samples were taken from white birches during their budding period as a novel phytoscreening approach. Birch sap sampling is shown to be a suitable means of characterizing contaminant distribution within the soil subsurface. Radial directional dependence of CVOC concentrations varies by almost 80% for tree core samples and 50% for birch sap samples. Variations in concentrations measured around the trunk do not, however, provide information on the inflow direction of contaminated groundwater. The weather conditions were shown to have a greater influence so that CVOC concentrations measured from samples taken during colder, rainier weather were, on average, a factor of 100 lower than those taken during a warm and dry period. Nevertheless phytoscreening is adequate for CVOC characterization in the soil subsurface if the campaign is carried out during a dry weather period, the results then can be taken as being semiquantitative.

Investigation on the removal of natural and synthetic estrogens using biofilms in continuous flow biofilm reactors and batch experiments analysed by gas chromatography/mass spectrometry.

The degradation of the natural estrogen 17ß-estradiol and the synthetic steroid hormone 17α-ethinylestradiol, two estrogens already detected in surface waters at low concentration levels, was investigated using continuous flow biofilm reactors and batch experiments. Biofilms in continuous flow experiments were created by natural organisms from river systems of the national park Unteres Odertal, Germany, whereas batch experiments were performed with isolated bacterial strains derived from biofilms. The analytical method, including solid phase extraction, silylation of analytes and measurement with GC/MS, was optimised for the target compounds 17ß-estradiol, 17α-ethinylestradiol and the possible metabolites estrone and estriol. The performance characteristics of the analytical method, namely recovery, standard deviations, method detection limits (MDL) and method quantification limits (MQL), were evaluated for accurate interpretation of degradation experiments. Continuous flow biofilm reactors were operated with two different nutrient media under dosage of estradiol and ethinylestradiol. Both estrogens were rapidly degraded within several hours; the metabolite estrone (from estradiol as well as from ethinylestradiol) was detected in significant amounts and was further decomposed. In additional batch experiments using isolated bacterial strains from the natural biofilms to decompose estradiol and ethinylestradiol, different metabolisms of isolates were explored. Five of the 15 isolated bacterial strains tested degraded estradiol and ethinylestradiol with different degradation rates. The results suggest that biofilms from national park Unteres Odertal possess a high capability to aerobically decompose natural and also synthetic estrogens so that these microorganisms could provide enhanced removal of pollutants in municipal water treatment plants.

Investigation of the microbial degradation of phenazone-type drugs and their metabolites by natural biofilms derived from river water using liquid chromatography/tandem mass spectrometry (LC-MS/MS).

The degradation of the pharmaceuticals phenazone and metamizole, two pyrazolone-derivates in widespread use, using biofilms created by natural organisms from the national park Unteres Odertal, Germany, were investigated. An analytical method based on LC-MS/MS was optimised to determine the substances phenazone and methylaminoantipyrine (MAA), the hydrolysis product of metamizole (also known as dipyrone), as well as their metabolites 1,5-dimethyl-1,2-dehydro-3-pyrazolone (DP), acetaminoantipyrine (AAA), formylaminoantipyrine (FAA) and 4-aminoantipyrine (AA). Performance characteristics of the method were evaluated in terms of recovery, standard deviation, coefficient of variation, method detection limits (MDL) and method quantification limits (MQL). Degradation studies of phenazone and MAA were conducted using a laboratory-scale continuous flow biofilm reactor fed with different nutrient media and with variable hydraulic retention times of 24 and 32 h. MAA was degraded rapidly to FAA and AA, while phenazone was not degraded under the prevailing conditions even after 32 h. By operating the bioreactor in batch mode to study the phenazone degradation potential of the biofilm under limiting nutrient conditions, an elimination rate of 85% phenazone was observed, but because of the slow elimination rate and aerobic conditions, the metabolite DP was not detected. In additional batch experiments using bacterial isolates from the natural biofilm to decompose phenazone, some bacterial strains were able to form DP from phenazone in marginal concentrations over the sampling period of eight weeks. Obviously, the microorganisms need a reasonably long time to adapt their metabolisms to enable the removal of phenazone from water samples.

Kinetics and organotropy of some polyfluorinated dibenzo-p-dioxins and dibenzofurans (PFDD/PFDF) in rats.

While polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDF) and the corresponding polybrominated congeners must be considered as animal teratogens and carcinogens, little information is available on corresponding polyfluorinated compounds (PFDD/PFDF). Kinetic studies on a few fluorinated dibenzo-p-dioxins and dibenzofurans revealed a rapid elimination, suggesting a much lower toxicity than the corresponding polychlorinated and polybrominated congeners. In order to obtain further clues on the possible toxicity, the kinetics and organ distribution (in liver, thymus and adipose tissue) of a PFDD/PFDF-mixture were studied in Wistar rats after intravenous application. The congeners investigated included four of the 2,3,7,8-substituted, and four of the not-2,3,7,8-substituted dibenzo-p-dioxins, as well as two dibenzofurans. The main result of our studies is the finding that the concentration in the thymus of several of the 2,3,7,8-substituted PFDD/PFDF greatly exceeded that in hepatic tissue. An organotropy quite different from that of the other polyhalogenated congeners must be expected, immunosuppressive effects presumably being the predominant ones. Overall, the elimination half-life of all the PFDD/PFDF studied is considerably shorter than that of the corresponding polychlorinated or polybrominated congeners, in the rat, suggesting a much lower toxicity in this species. No information is available for other species, e.g. nonhuman primates or humans.

Analysis of chlorinated paraffins in cutting fluids and sealing materials by carbon skeleton reaction gas chromatography.

Chlorinated paraffins (CPs) pose a major risk in the environment, due to their wide application, to their persistence, to their carcinogenic potential, and in view of the fact, that they cannot be easily identified. Various commercial cutting fluids and sealing materials were analysed for CPs with carbon skeleton reaction gas chromatography (GC) and flame ionization detection. CPs are simultaneously dechlorinated and hydrogenated to the corresponding alkanes with Pd catalyst material in the GC injector. With this method, the carbon chain length of commercial technical CPs was determined. In six of sixteen sealing materials we found five short and one medium chain length polychlorinated paraffins in percentages of 9-16% (w/w). In five cutting fluids we found predominantly medium to long chain length chloroparaffins with percentages of 2.5-31% (w/w), only one fluid contained short chain CPs.