Monitoring of iodinated X-ray contrast media in surface water

A monitoring programme was carried out in order to determine iodinated X-ray contrast media (ICM) in the River Danube and to investigate the raw water quality for drinking water production at Langenau waterworks. The study revealed that the maximum concentrations of ICM (over 500 ng l(-1) for diatrizoic acid and iopamidol) were found in 2h-composite samples taken from the downstream of the Ulm/Neu-Ulm metropolitan area. By means of a concentration profile over one month the highest ICM concentrations were observed on weekdays. The extended data evaluation with principal component analysis shows that the upstream and downstream samples had different pattern of variations in ICM concentration and also demonstrates a clear change in ICM composition by the discharge of municipal wastewater. In addition to load profiles of ICM, time-dependent plots of principal component 1 exhibited peaks, indicating a short-term discharge of ICM between the two sampling sites. In conclusion, a point source for ICM contamination between the sampling sites in Ulm upstream and Leipheim downstream seems to be the reasonable explanation for peak ICM concentrations. Due to the observed high variations of ICM concentrations in river, the evaluation of natural waters by means of a single analysis is not representative.     

Biotransformation of metamitron by human p450 expressed in transgenic tobacco cell cultures

In the present investigation, the oxidative metabolism of 14C-labeled metamitron was examined in plant cell cultures of tobacco overexpressing human P450 enzymes CYP1A1 or CYP1A2; special interest was in the aromatic hydroxylation of the herbicide. The oxidative metabolites deaminometamitron (DAM) and 4-hydroxydeaminometamitron (4-HDAM) were found in the untransformed control culture as well as in the transgenic culture. The transgenic cultures, however, exhibited higher turnover rates after 48 h of incubation with 20 microg 14C-metamitron per assay (untransformed: 40%, CYP1A1: 80%, CYP1A2: 100%). Primary metabolite 4-HDAM was partially found in glucosylated form in the transgenic cultures. As minor oxidative metabolites, 6-hydroxyphenyl-3-methoxymethyl-1,2,4-triazine-5(4H)-one and 3-hydroxymethyl-6-phenyl-1,2,4-triazine-5(4H)-one were identified in the transgenic cultures by GC-MS, LC-MS. Additionally, it could be demonstrated that both foreign enzymes (CYP1A1, CYP1A2) also catalyzed the deamination of metamitron. In a large-scale study (up to 400 microg per assay) with the transgenic culture expressing CYP1A2, the high efficiency of this P450 system toward metamitron was demonstrated: turnover of the xenobiotic was almost complete with 400 microg. Since large portions of unglucosylated 4-H-DAM were found, the activity of foreign CYP1A2 apparently exceeded that of endogenous O-glucosyltransferases of the tobacco cell culture. We concluded that in comparison to the nontransformed cell culture, the extent of metabolism was considerably higher in the transgenic cultures. The transgenic cell cultures expressing human CYP1A1 or CYP1A2 are thus suitable tools for the production of large quantities of primary oxidized metabolites of metamitron.     

UV-Filtersubstanzen in Wasser und Fischen

A method was developed for the analysis of fish samples to detect sunscreen agents (SSA) together with organochlorides (PCB, DDT) in different fish tissues. Detection limits of the compounds analyzed are in the range of ng/kg and vary between 40 and 90 ng/kg fillet. Recovery rates range from 78 to 104%. The contamination of water and fish with SSA in Meerfelder Maar lake, the Eifel, Germany was investigated in 1991 and 1993 and allowed the identification and quantification of six different SSA in the fish. The sum of SSA concentrations in perch taken in the summer of 1991 was 2.0 mg/kg lipid and 0.50 mg/kg lipid was found in roach sampled during the summer of 1993. Both species were contaminated with SSA and organochlorides to the same ranges as PCB and DDT. Even in the fillet of roach taken from three other lakes in Germany, methylbenzylidene camphor, a lipophilic SSA, was detected. These results indicate that SSA are wide-spread in German lakes. Therefore, they can be seen as a new group of relevant environmental chemicals. In the investigated lakes, the concentrations of the SSA in water were mostly below the detection limits. Thus, fish can be used as a biomonitor for these lipophilic compounds. Due to the lack of toxicological data for aquatic organisms, an ecotoxicological assessment is impossible at the moment.     

Nitrate storage by phytoplankton in a coastal upwelling environment

The storage of nitrate by phytoplankton cells during the early phases of upwelling was studied in coastal stations off northern Spain (southern Bay of Biscay) between 1990 and 1994. In this region, a persistent upwelling during summer is characterised by intermittent pulses of variable intensity, and increased nutrient concentrations in the surface layer. The main effect of an upwelling pulse on phytoplankton distribution is the shifting of the chlorophyll a and primary production maxima to near the surface. When the upwelling relaxes, thermal stratification of the water column occurs, and a distinct subsurface chlorophyll maximum develops below the production maximum. An accumulation of intracellular nitrate characterized the early phases of upwelling (mean = 2.73 μmol N m⁻³), maximum concentrations being attained at depths where biomass and production values were moderate. In contrast, phytoplankton cells from non-upwelling situations contained significantly lower concentrations of intracellular nitrate (mean = 0.17 μmol N m⁻³). The variations in the intracellular pool of nitrate may result from the differential allocation of resources within the cell as a result of variations in the energy available, since the uptake and assimilation of nitrate is a relatively expensive process involving several enzymatic systems. We hypothesize that nitrate storage by phytoplankton cells is characteristic of early phases of upwelling and is linked to patterns of carbon fixation. Average nitrogen budgets for upwelling and non-upwelling situations indicate that intracellular nitrate reserves are not responsible for maintaining high phytoplankton growth rates, since they only account for <2% of daily primary production during upwelling events. Received: 28 August 1996 / Accepted 3 December 1996     

Determination of atrazine in rainfall and surface water by enzyme immunoassay

Rainwater and surface water from four sites in Germany (Bavaria and Lower Saxony) were analyzed for atrazine by enzyme immunoassay from June 1990 until October 1992. The limit of quantification of the immunoassay was 0.02 μg/L with a middle of the test at 0.2 μg/L. About 60 % of the samples contained measurable amounts of atrazine. Seasonal trends were observed, with the highest concentration in the summer months of up to 4 μg/L for rainwater and up to 15 μg/L for surface waters. The highest concentrations were found in agricultural areas, while in the investigated national parks up to 0.56 μg/L could be detected in rain water. This points to long-range atmospheric transport from agricultural areas to pristine national parks. Samples from forest stands usually showed higher atrazine concentrations than samples from open fields. Deposition rates of 10 – 50 μg/m² · yr were observed in the national parks and 10–180 μg/m² · yr at the agricultural sites. Comparison of results obtained by enzyme immunoassay and GC/MS showed a good correlation of r = 0.95.     

Nitrate in groundwater: an isotopic multi-tracer approach

In spite of increasing efforts to reduce nitrogen inputs into groundwater from intensive agriculture, nitrate (NO3) remains one of the major pollutants of drinking-water resources worldwide. Determining the source(s) of NO3 contamination in groundwater is an important first step for improving groundwater quality by emission control, and it is with this aim that we investigated the viability of an isotopic multi-tracer approach (delta15N, delta11B, 87Sr/86Sr), in addition to conventional hydrogeologic analysis, in two small catchments of the Arguenon watershed (Brittany, France). The main anthropogenic sources (fertilizer, sewage effluent, and hog, cattle and poultry manure) were first characterized by their specific B, N and Sr isotope signatures, and compared to those observed in the ground- and surface waters. Chemical and isotopic evidence shows that both denitrification and mixing within the watershed have the effect of buffering NO3 contamination in the groundwater. Coupled delta11B, delta15N and 87Sr/86Sr results indicate that a large part of the NO3 contamination in the Arguenon watershed originates from the spreading of animal manure, with hog manure being a major contributor. Point sources, such as sewage effluents, contribute to the NO3 budget of the two watersheds.