Frank Sacher

Pharmaceuticals in groundwaters: Analytical methods and results of a monitoring program in Baden-Württemberg, Germany

In this paper, analytical methods for the trace-level determination of 60 pharmaceuticals in aqueous samples are presented. The list of compounds amenable to the methods comprises analgesics, antiphlogistics, antirheumatics, beta-blockers, broncholytics, lipid-lowering agents (or their metabolites), antiepileptics, vasodilators, tranquillizers, antineoplastic drugs, iodinated X-ray contrast media, and antibiotics of different kind, mainly sulfonamides, macrolides, and penicillins. All methods are based on automated solid-phase extraction followed by GC-MS (after derivatization of the acid compounds) or HPLC-electrospray ionization MS-MS. After an intense validation, which included the determination of performance data according to the German standard method DIN 32645 (limit of detection, limit of identification, limit of determination), the determination of linearity, recovery, and repeatability and the study of matrix effects, the analytical methods were applied within a monitoring program on the occurrence of pharmaceuticals in groundwaters of Baden-Württemberg. During this monitoring program, it was found that several of the compounds under investigation could be detected in groundwaters and their occurrence could be traced back to an impact of municipal or industrial waste water.

Analysis of primary and secondary aliphatic amines in waste water and surface water by gas chromatography-mass spectrometry after derivatization with 2,4-dinitrofluorobenzene or benzenesulfonyl chloride

Two methods for the determination of aliphatic amines such as methylamine, dimethylamine, ethylamine, diethylamine, piperidine, pyrrolidine or morpholine in waste water and surface water at the sub-ppb level are presented. The methods are based on a derivatization of the amines within the aqueous medium with 2,4-dinitrofluorobenzene and benzenesulfonyl chloride, respectively. In both cases the derivatives are extracted with dichloromethane and measured by GC-MS. The performance data of the two methods are compared and the method which is based on the derivatization with benzenesulfonyl chloride is finally applied to industrial waste waters and surface waters in order to determine the rate of occurrence of aliphatic amines in the aquatic environment.

Comparison of five in vitro bioassays to measure estrogenic activity in environmental waters

Bioassays are well established in the pharmaceutical industry and single compound analysis, but there is still uncertainty about their usefulness in environmental monitoring. We compared the responses of five bioassays designed to measure estrogenic activity (the yeast estrogen screen, ER-CALUX, MELN, T47D-KBluc, and E-SCREEN assays) and chemical analysis on extracts from four different water sources (groundwater, raw sewage, treated sewage, and river water). All five bioassays displayed similar trends and there was good agreement with analytical chemistry results. The data from the ER-CALUX and E-SCREEN bioassays were robust and predictable, and well-correlated with predictions from chemical analysis. The T47D-KBluc appeared likewise promising, but with a more limited sample size it was less compelling. The YES assay was less sensitive than the other assays by an order of magnitude, which resulted in a larger number of nondetects. The MELN assay was less predictable, although the possibility that this was due to laboratory-specific difficulties cannot be discounted. With standardized bioassay data analysis and consistency of operating protocols, bioanalytical tools are a promising advance in the development of a tiered approach to environmental water quality monitoring.

Occurrence of the antidiabetic drug metformin in sewage and surface waters in Germany

The antidiabetic drug metformin is among the pharmaceuticals with the highest production numbers world-wide. This paper presents first data on the occurrence of metformin in sewage and surface waters in Germany. Analysis of metformin is based on pre-concentration of the analyte onto a polymeric solid-phase material and subsequent determination by liquid chromatography and tandem mass spectrometry. Applying the method to sewage and surface waters, recoveries >90% and limits of detection of 10 ng L(-1) could be achieved by pre-concentration of a sample volume of only 10 mL. Measurements in sewage and surface waters showed an almost ubiquitous presence of metformin in the aquatic environment. The measured concentration levels in sewage treatment plant influents correlate nicely to the prescription numbers for metformin in Germany. During sewage treatment a significant reduction of metformin concentrations was observed which seems to be mainly due to microbial degradation. Despite this significant elimination during sewage treatment, metformin was found in all river waters under investigation. Concentration levels depend on the sewage fraction of the receiving waters and for most rivers are in the range of several 100 ng L(-1), i.e. in the same order of magnitude or even higher than for other relevant pharmaceutical residues.

Selection of organic process and source indicator substances for the anthropogenically influenced water cycle

An increasing number of organic micropollutants (OMP) is detected in anthropogenically influenced water cycles. Source control and effective natural and technical barriers are essential to maintain a high quality of drinking water resources under these circumstances. Based on the literature and our own research this study proposes a limited number of OMP that can serve as indicator substances for the major sources of OMP, such as wastewater treatment plants, agriculture and surface runoff. Furthermore functional indicators are proposed that allow assessment of the proper function of natural and technical barriers in the aquatic environment, namely conventional municipal wastewater treatment, advanced treatment (ozonation, activated carbon), bank filtration and soil aquifer treatment as well as self-purification in surface water. These indicator substances include the artificial sweetener acesulfame, the anti-inflammatory drug ibuprofen, the anticonvulsant carbamazepine, the corrosion inhibitor benzotriazole and the herbicide mecoprop among others. The chemical indicator substances are intended to support comparisons between watersheds and technical and natural processes independent of specific water cycles and to reduce efforts and costs of chemical analyses without losing essential information.

MTBE (methyl tertiary-butyl ether) in groundwaters: Monitoring results from Germany

In Germany information on the occurrence of MTBE in groundwaters is scarce. In order to assess the German situation, in 1999 a monitoring programme on MTBE in groundwater was set up. Within this survey 170 wells were examined, which are used as groundwater monitoring points or which are foreseen for drinking water extraction in emergency cases or for irrigation purposes. In rural areas MTBE was found only in 9% of all samples in concentrations above the limit of determination (LOD) of 0.05 microg L(-1). In urban areas MTBE was detected in 49% of all wells under investigation and the median concentration was calculated to 0.17 microg L(-1). In one case a maximum MTBE concentration of almost 700 microg L(-1) was detected. As a first result of this survey one can conclude, that MTBE is regularly present in German groundwaters under urban areas. Although investigations about the occurrence of MTBE in German groundwaters have to be extended in future, this first snapshot can lead to the assumption, that MTBE concentrations due to diffuse sources are lower than the ones found in the USA. Nevertheless, e.g. accidental spills can lead to elevated MTBE concentrations.

Polar nitrogen compounds and their behaviour in the drinking water treatment process.

Aliphatic and alicyclic amines as well as ethanolamines are extremely polar compounds, frequently found in the environment, and some of them have high toxicity. To address the contamination of selected German surface waters examined and the importance of bank filtration in Eastern Germany, investigations on the behaviour of polar organic nitrogen compounds during water treatment were carried out. Test conditions were designed appropriately for drinking water treatment conditions, and the tests were carried out using model water as well as bank filtrate. Test filter studies of microbial degradation of selected compounds demonstrated the following order of biodegradability: ethanolamine > dimethylamine > pyrrolidine > ethylenediamine. piperidine > diethylamine > morpholine > piperazine > cyclohexylamine. Flocculation tests using iron salts as well as aluminium salts as coagulants showed very low removal rates for the amines. The best results for the removal of the polar organic nitrogen compounds from the water were obtained using ozonation. Based on the reaction-rate constants, the order of degradation by ozone is: piperazine > morpholine > ethylenediamine > piperidine, cyclohexylamine > dimethylamine > ethanolamine > pyrrolidine > diethylamine. Disinfection by chlorine-containing agents under drinking water treatment conditions did not give effective elimination of the selected polar nitrogen compounds.

SchussenAktivplus: reduction of micropollutants and of potentially pathogenic bacteria for further water quality improvement of the river Schussen, a tributary of Lake Constance, Germany

The project focuses on the efficiency of combined technologies to reduce the release of micropollutants and bacteria into surface waters via sewage treatment plants of different size and via stormwater overflow basins of different types. As a model river in a highly populated catchment area, the river Schussen and, as a control, the river Argen, two tributaries of Lake Constance, Southern Germany, are under investigation in this project. The efficiency of the different cleaning technologies is monitored by a wide range of exposure and effect analyses including chemical and microbiological techniques as well as effect studies ranging from molecules to communities.

Efficiency of Ozonation and AOP for Methyl-tert-Butylether (MTBE) Removal in Waterworks

Methyl-tert-butylether (MTBE) is attracting more and more attention since it was discovered in groundwater and other raw water sources for waterworks and proved to difficult to remove during conventional treatment steps in drinking water production. Therefore advanced treatment processes have to be evaluated in addition to established treatment technologies. Laboratory based experiments were carried out studying ozonation with varying ozone concentrations at different pH values. For the elimination of MTBE the degradation through hydroxyl radicals was identified as the main degradation pathway. No decline of MTBE concentration occurred in experiments with molecular ozone, but AOP (Advanced Oxidation Processes) experiments where hydrogen peroxide (H2O2) was added showed a more efficient elimination. However, no complete mineralization was achieved — tert-butyl alcohol (tBA) and tert-butyl formate (tBF) were identified as metabolites. In natural waters (i.e., groundwater, bank filtrated water, and drinking water) the efficiency of MTBE removal was strongly dependent on the content of natural organic matter and alkalinity because of their scavenging characteristics. However, bromate formation was observed as well and could cause problems for drinking water production. Comparison with data gained from waterworks showed that conventional ozonation techniques as applied in waterworks are not able to remove MTBE efficiently.

Minimization Of Disinfection By-Products Formation In Water Purification Process Using Chlorine Dioxide — Case Studies

Abstract The formation of the by-product chlorite after using chlorine dioxide for the disinfection of drinking water depends on the quantity of the organic matter dissolved in the water. A further decisive factor for the chlorite formation is the level of residual free chlorine dioxide. The chlorine dioxide demand decreases by application of activated carbon filtration, especially after the use of a combination of ozone and activated carbon treatment of the water. Nevertheless, higher chlorine dioxide residuals are a source of chlorite and chlorate formation. The concept of the “Minimum Chlorine Dioxide Dosage (MCDD)” is developed in order to give a clue to the water companies for an optimized chlorine dioxide dose without compromising the disinfection efficiency. By application of the MCDD, the residual level of chlorine dioxide is focused to 0.05 mg/L after 0.5 h contact time. In the range of the MCDD the ratio of the chlorite formation and the chlorine dioxide demand is nearly independent of the level of DOC.