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A simple classification scheme is suggested to characterize the biological degradation of micropollutants such as pharmaceuticals, musk fragrances and estrogens during wastewater treatment. The scheme should be a basis for the discussion about potential removal efficiencies. Hence, the biological degradation of 25 pharmaceuticals, hormones and fragrances was studied in batch experiments at typical concentration levels using activated sewage sludge originating from nutrient-eliminating municipal wastewater treatment plants. Since pseudo first-order degradation kinetics was observed for all compounds down to ng L(-1) levels, the removal rates can be predicted for various reactor configurations. Therefore dilution of wastewater (e.g. by extraneous water) is expected to reduce the degree of biological removal. Wastewater segregation and treatment at the source are therefore to be favoured for elimination of persistent micropollutants over centralized end-of-pipe treatment. For reactor configurations typical for nutrient removal in municipal wastewater, the derived formula for predicting removal allows the identification of three groups of micropollutants according to their degradation constant k(biol): compounds with k(biol)0.1 L g(SS)(-1)d(-1) are not removed to a significant extent (20%), compounds with k(biol)10 L g(SS)(-1)d(-1) transformed by90% and in-between moderate removal is expected. Based on the degradation of a heterogeneous group of 35 compounds (including literature data), state of the art biological treatment schemes for municipal wastewater are not efficient in degrading pharmaceuticals: only 4 out of 35 compounds are degraded by more than 90% while 17 compounds are removed by less than 50%.

Pressurized liquid extraction (PLE) was optimized and validated for the determination of sulfonamide and macrolide antimicrobials and trimethoprim in sewage sludge samples. A mixture of water/methanol (50:50, v/v) was found as the most efficient extraction solvent. A temperature of 100 degrees C and a pressure of 100 bar were chosen for extraction. Two cycles of 5 min each efficiently extracted at least 97% of the total extractable amount of all studied analytes from activated sludge. The limits of quantification (S/N= 10) varied between 3 and 41 microg/kg dry weight (dw) and the relative recoveries ranged between 78 and 142%. Additionally, the influence of pH and different LC/MS/MS systems on the absolute recoveries was assessed. Of the investigated antimicrobials sulfapyridin, sulfamethoxazole, trimethoprim, azithromycin, clarithromycin and roxithromycin were detected in municipal sewage sludge samples. Concentrations in activated sludge ranged up to 197 microg/kgdw. In comparison, results obtained by ultrasonic solvent extraction were significantly lower for sulfonamides and in tendency lower for macrolides.

The removal of seven pharmaceuticals and two fragrances in the biological units of various full-scale municipal wastewater treatment plants was studied. The observed removal of pharmaceuticals was mainly due to biological transformation and varied from insignificant (10%, carbamazepine) to90% (ibuprofen). However, no quantitative relationship between structure and activity can be set up for the biological transformation. Overall, it can be concluded that for compounds showing a sorption coefficient (K(d)) of below 300 L kg(-1), sorption onto secondary sludge is not relevant and their transformation can consequently be assessed simply by comparing influent and effluent concentrations. The two fragrances (HHCB, AHTN) studied were mainly removed by sorption onto sludge. For the compounds studied, comparable transformation and sorption was seen for different reactor types (conventional activated sludge, membrane bioreactor and fixed bed reactor) as well as for sludge ages between 10 and 60-80 days and temperatures between 12 degrees C and 21 degrees C. However, some significant variations in the observed removal currently lack an explanation. The observed incoming daily load of iopromide and roxithromycin in medium-sized municipal wastewater treatment plants (up to 80,000 population equivalents) is generated by only a small number of patients: the consequences for representative 24h composite sampling are discussed. Generally, the paper presents a method for setting up mass balances for micropollutants over entire wastewater treatment plants, including an estimation of the accuracy of the quantified fate (i.e. removal by sorption and biological transformation).

The occurrence of sulfonamide and macrolide antimicrobials, as well as trimethoprim, was investigated in conventional activated sludge treatment. Average daily loads in untreated wastewater correlated well with those estimated from annual consumption data and pharmacokinetic behavior. Considerable variations were found during a day, and seasonal differences seem to occur for the macrolides, probably caused by a higher consumption of these substances in winter. The most predominant macrolide and sulfonamide antimicrobials were clarithromycin and sulfamethoxazole, respectively. In the case of sulfamethoxazole, the main human metabolite, N4-acetylsulfamethoxazole, was included as an analyte, accounting for up to 86% of the total load in untreated wastewater. The results obtained illustrate the importance of considering retransformable substances, for example human metabolites, when investigating the behavior and fate of pharmaceuticals. Average concentrations of sulfapyridine, sulfamethoxazole, trimethoprim, azithromycin, and clarithromycin in activated sludge ranged between 28 and 68 microg/kg of dry weight. Overall the sorption to activated sludge was shown to be low for the investigated antimicrobials, with estimated sorption constants for activated sludge below 500 L/kg. Elimination in activated sludge treatment was found to be incomplete for all investigated compounds. In final effluents, the median concentrations for sulfamethoxazole and clarithromycin were 290 and 240 ng/L, respectively.

The elimination of sulfonamides, macrolides and trimethoprim from raw wastewater was investigated in several municipal wastewater treatment plants. Primary treatment provided no significant elimination for the investigated substances. Similar eliminations were observed in the secondary treatment of two conventional activated sludge (CAS) systems and a fixed-bed reactor (FBR). Sulfamethoxazole, including the fraction present as N 4 -acetyl-sulfamethoxazole, was eliminated by approximately 60% in comparison to about 80% in a membrane bioreactor (MBR) independently of the solid retention time (SRT), indicating a positive correlation of the observed elimination to the organic substrate concentration. The elimination for macrolides and trimethoprim varied significantly between the different sampling campaigns in the two CAS systems and in the FBR. In the MBR, these analytes were eliminated up to 50% at SRT of 16 ± 2 and 33 ± 3 d. Trimethoprim, clarithromycin and dehydro-erythromycin showed a higher elimination of up to 90% at a SRT of 60–80 d indicating a correlation with reduced substrate loading (SL). Together with the high SRT, the SL may lead to an increased biodiversity of the active biomass, resulting in a broader range of degradation pathways available. Two investigated sand filters showed different elimination behavior. One led to a significant elimination of most macrolides (17–23%) and trimethoprim (74 ± 14%), while no elimination was observed in the other sand filter investigated.

To reduce the release of pharmaceuticals and endocrine disruptors into the aquatic environment or to remove them from wastewater intended for direct or indirect reuse, the application of advanced wastewater treatment may be required. In the present study, municipal wastewater effluents were treated with ozone (O3) in a pilot-scale plant consisting of two bubble columns. The investigated effluents, which varied in suspended solids concentrations, comprised an effluent of conventional activated sludge treatment (CAS), the same effluent dosed with 15 mg of TSS L(-1) of activated sludge (CAS + SS), and the effluent of a membrane bioreactor pilot plant (MBR). Selected classes of pharmaceuticals were spiked in the wastewater at realistic levels ranging from 0.5 to 5 microg L(-1). Samples taken at the inlet and the outlet of the pilot plant were analyzed with liquid chromatography (LC)-electrospray tandem mass spectrometry (MS). Macrolide and sulfonamide antibiotics, estrogens, and the acidic pharmaceuticals diclofenac, naproxen, and indomethacin were oxidized by more than 90-99% for O3 dosesor = 2 mg L(-1) in all effluents. X-ray contrast media and a few acidic pharmaceuticals were only partly oxidized, but no significant differences were observed among the three effluents. These results show that many pharmaceuticals present in wastewater can be efficiently oxidized with O3 and that suspended solids have only a minor influence on the oxidation efficiency of nonsorbing micropollutants.

An analytical method has been developed and validated for the simultaneous trace determination of four macrolide antibiotics, six sulfonamides, the human metabolite N4-acetylsulfamethoxazole, and trimethoprim in wastewater. The method was validated for tertiary, secondary, and-unlike in previously published methods-also for primary effluents of municipal wastewater treatment plants. This wide range of application is necessary to thoroughly investigate the occurrence and fate of chemicals in wastewater treatment. Wastewater samples were enriched by solid-phase extraction, followed by reversed-phase liquid chromatography coupled to tandem mass spectrometry using positive electrospray ionization. Recoveries from all sample matrixes were generally above 80%, and the combined measurement uncertainty varied between 2 and 18%. Concentrations measured in tertiary effluents ranged between 10 ng/L for roxithromycin and 423 ng/L for sulfamethoxazole. Corresponding levels in primary effluents varied from 22 to 1450 ng/L, respectively. Trace amounts of these emerging contaminants reach ambient waters, since all analytes were not fully eliminated during conventional activated sludge treatment followed by sand filtration. In the case of sulfamethoxazole, the amount present as human metabolite N4-acetylsulfamethoxazole had to be taken into account in order to correctly assess the fate of sulfamethoxazole in wastewater treatment.