Über das Vorkommen von Pestiziden im Trinkwasser und in der Nahrung Pesticides in Drinking Water and Food

Amounts of pesticide residues determined in drinking water and in food during the last decade are compared. Whereas in drinking water pesticides were determined in concentrations of about 0.1 μg/L, the pesticide contents of fruits and vegetables were higher by a factor of 100 to 10000. Even in the grease fraction of mother's milk pesticides were found in the mg/kg range. These results may help to do the classification of drinking water as a possible health hazard concerning pesticides.     

Vorkommen natürlicher und synthetischer östrogener Steroide in Wässern des süd‐ und mitteldeutschen Raumes

Distribution of Natural and Synthetic Estrogenic Steroid Hormones in Water Samples from Southern and Middle Germany Natural and synthetic hormones can reach surface waters via domestic sewage effluents. For drinking water production, bank filtration of river waters is a common procedure and hormone contaminations can potentially reach groundwater levels and drinking water sources. In order to analyse steroid hormones in the different aquatic compartments (raw sewage and effluent, surface water, groundwater, raw and drinking water) of South and Middle Germany, a sensitive analytical method was developed and employed to detect the natural steroid hormones estradiol (E2) and estrone and the synthetic estrogen ethinylestradiol (EE2). Samples which were taken in two subsequent series were subjected to clean‐up and enrichment procedure and subsequently analysed by HPLC‐MS. The limit of quantitation for the method was determined to be 0.05 to 0.5 ng/L, depending on the matrix. By treating the samples with glucuronidases/arylsulfatases, conjugates were amenable to analysis and the sum of conjugates and unconjugated steroids was calculated. In raw sewage, the median of the concentrations of the unconjugated steroids was 7 ng/L for EE2, 1.5 ng/L for E2, and 5.5 ng/L for estrone. After cleavage of conjugates, the medians of total steroids were 9.5 ng/L (EE2), 3 ng/L (E2), and 13 ng/l (estrone). Conjugates therefore contributed up to 50 % of the total steroid concentration in raw sewage. In treated effluents, the concentrations of steroids were much lower than in the raw sewage. The medians of free steroids were determined to be 0.3 ng/L for EE2, 0.2 ng/L for E2, and 2.5 ng/L for estrone. Overall the medians in the effluent were thus less than 10% of those in the influent. Conjugates still contributed significantly (40% and more) to the steroid concentrations (medians: EE2: 0.5 ng/L, E2: 0.8 ng/L, and estrone: 8 ng/L).     

Die gaschromatographische Bestimmung von Diethylentriaminpentaessigsäure in Oberflächenwasser

Gaschromatographic Determination of Diethylenetriaminepentaacetic Acid in Surface Water. A method for the determination of diethylenetriaminepentaacetic acid (DTPA) is reported. The determination is based on the preconcentration on a strong base anion exchange resin, esterification with n-propanol and following gaschromatographic separation using a N-selective detector. The sensitivity of the method, including enrichment, is 1 μg/L in river water. The identity of DTPA in river water was proved by mass spectrography. The method can be used also for the quantitative determination of nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), cyclohexanediaminetetraacetic acid (CDTA) and ethyleneglycolbis-(2-aminoethylether)-N,N,N′,N′-tetraacetic acid (EGTA). The method was used to examine river water. An investigation along the river Rhine, taking grab samples from January and february 1992 showed that DTPA was present in some sampling places in similiar concentrations as NTA and EDTA.     

Entwicklung von Enzymimmunoassays zum Nachweis von Phenoxycarbonsäure-Herbiziden in Trink- und Grundwässern Development of Enzyme Immunoassays for the Detection of Phenoxycarboxylic Acid Herbicides in Drinking Water and Groundwater

Competitive solid phase enzyme immunoassays using polyclonal antibodies were developed for the detection of the phenoxycaboxylic acids MCPB [4-(4-chloro-2-methylphenoxy)butyric acid], Mecoprop [2-(4-chloro-2-methylphenoxy)propionic acid], and 2,4-D [(2,4-dichloro-phenoxy)acetic acid] in drinking water and ground water. The carrier protein for the immunization was bovine serum albumin, horseradish peroxidase conjugates were employed as enzyme tracer. For the three antisera, the optimization of detection limits and test sensitivities was our first consideration. For the mecoprop and 2,4-D antisera, the strongest influences were the pH value and the ionic strength, as much as the use of enzyme tracers with lower affinities. The MCPB antiserum reacted with 2,4-DB[4-(2,4-dichlorophenoxy)butyric acid] with equal specificity, either could be detected at 0.02 μg/L (80% B/B₀), middle of the test (50 B/B₀) lying at 0.1 μg/L. The detection limit with mecoprop antiserum was optimized to 0.02 μg/L, the prescribed limit for drinking water of 0.1 μg/L ling at 60 % B/B₀. The strongest cross-reactivity was found for mecoprop methyl ester. MCPB. 2,4-DB, and dichloroprop have crossreactivities of 50%, 6.7%, and 6.3%, respectively. The 2,4-D antiserum reacts less sensitively with 2,4-D, the detection limit being 0.4 μg/L. The 2,4-D isooctyl ester and 2,4-D methyl ester demonstrate as cross-reacting compounds high cross-reactivites of 3630% and 2230%. The cross-reactions of the compounds 2,4-DB, MCPB, and MCPA [(4-chloro-2-methylphenoxy)acetic acid] lie at 52%, 69%, and 41%. 100 ground water tests were spiked within laboratory. All positive samples were correctly identified. Falsely negative results did not appear.     

TOC-Bestimmung in Schlämmen,Sedimenten und Schwebstoffen — Beschreibung des Verfahrens und begleitender Qualitätssicherungsmaßnahmen Determination of TOC in Sludge,Sediment and Suspended Solids — Description of the Analytical Procedure and Accompanying Quality Control Procedures

The total organic carbon (TOC) is calculated by subtracting the inorganic carbon (IC) from the total carbon (TC). For TC determination, the carbon in a sample is completely converted to CO₂ by decomposition/combustion in an oxygen stream. To determine IC, inorganic carbon (carbonate) is liberated by adding acid and by heating in an oxygen stream. In both cases, CO₂ is quantified by infrared spectrometry. To gain reliable and reproducable results for sludge, sediment and suspended solids, at least the following conditions have to be met: particle size has to be smaller than 200 μm; weightout has to be selected in such a way, that the signal area is not below and the signal maximum is not above specific instrument dependent parameters; combustion/decomposition has to be complete (TC: ≥ 1300 °C, no soot) and rules for analytical quality assurance must be followed. The TC quantification of calcium carbonate is used for system calibration. Daily working procedures include calibration checks by mean control charts for TC determination of calcium carbonate and IC determination of sodium carbonate as well as for control sediment TC and IC quantifications.     

UV-Derivativ-Spektren zur Vorabschätzung des Gehaltes von polycyclischen aromatischen Kohlenwasserstoffen in Schwebstoffen und Sedimenten der Gewässer Derivative UV Spectra for Estimating the Contents of Polycyclic Aromatic Hydrocarbons in Suspended Solids and Sediments of Waters

By means of UV spectra of cyclohexane extracts from aquatic sediments it is possible to distinguish: “normal” mineral oil aromatics (e. g. of the middle distillation fraction), used oils, and highboiling raffinates, tar oils, and — as representative of aromatics listed in the German drinking water ordinance — fluoranthene. Starting with less selective extractants and the basic UV spectra, it is shown that spectra of higher orders frequently allow a quantitative determination of fluoranthene. If it is justified to assume a constant conversion factor, the result of the measurement can be used to calculate the contents of the whole group of aromatics listed in the German drinking water ordinance. A comparison with other methods (HPLC etc.) and with results from other laboratories showed good agreement. Finally, the diagnostic capacity (fingerprint) of derived spectra is pointed out.     

Biosilicium (BSi) in Sedimenten Mecklenburger Seen (Deutschland) und das Calciumcarbonat-Biosilicium-Verhältnis als Trophie- und Wasserstandsindikator Biogenic Silica (BSi) in Sediments of the Mecklenburgian Lake District (Germany) and the Calcite-Silica-Relation as Indicator for Trophy and Water Level

The BSi content has been investigated in the surface sediments of lakes of different trophic state in the Mecklenburgian Lake District. The BSi content differs between 1 to 1000 mg BSi/g dry matter. High values were found in deep eutrophic lakes. Litoral sediments and shallow eutrophic lakes have lower contents. BSi content was found to be correlated with lake morphometry, depth, trophic level, sediment composition and especially with calcite. With the CaCO₃/BSi-value, 3 groups of lakes can be characterized:

• CaCO₃/BSi = 0 oligotrophic and dystrophic lakes
• CaCO₃/BSi ≤ 10 mesotrophic and eutrophic deep lakes
• CaCO₃/BSi ≤ 10 eutrophic shallow lakes

The results from the recent sediments have been compared with those from older sediments. Using the CaCO₃/BSi-value, climatic change, trophic state, and sea level can be detected.