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Ozonation has been used to effectively remove micropollutants from the secondary effluent in several wastewater treatment plants. It is known that ozonation transforms tertiary amine compounds into their respective N-oxides, however in an earlier study a mass balance could not be closed at elevated ozone concentrations, leading to the assumption that more ozonation products are possible. This study was conducted to elucidate which (hitherto unknown) ozonation products can be formed from venlafaxine and tramadol when ozonating wastewater. Ozonation experiments were performed with tramadol and venlafaxine N-oxide in two different set-ups. Both tramadol- and venlafaxine N-oxide degraded during ozonation in pure (deionized) water in both semi-continuous and batch mode ozonation set-ups. 13 and 17 new transformation products were detected from tramadol- and venlafaxine N-oxide respectively, using high resolution mass spectrometry with ESI(+) ionization. Empirical chemical formulas were proposed based on the determination of the exact masses and interpretation of the product ion spectra. These transformation products result from the addition of one to three oxygen atoms and removal of C, –CH2, C2H2, C3H6, etc., from the parent molecule, respectively. Quenching experiments suggested that most of the transformation products originated from the direct reaction with ozone (eight for tramadol N-oxide and ten for venlafaxine N-oxide), whereas fewer products originated from the reaction with OH radicals (three for tramadol N-oxide and three for venlafaxine N-oxide). Reaction mechanisms and chemical structures of products are proposed, based on the available active sites and past literature on ozone reaction mechanisms. The experimental results are compared to theory and literature on ozone reactive sites and ozone reaction mechanisms. All in all this shows that there can be multiple ozonation products, and ozonation pathways can be complex, even if initially only one ozonation product is formed.

Advanced treatment technologies for the removal of pharmaceuticals and other organic micropollutants inWWTPs primarily target the removal of parent compounds. Nevertheless, the removal of metabolites originatingfrom human- or microbial metabolism during biological treatment needs comparable consideration, as some ofthem might be present in high concentrations and contribute to toxicity.This study was conducted to elucidate the removal of human and microbial metabolites of pharmaceuticals as afunction of the specific ozone dose. Ozonation was performed on four sites with two pilot- and two full-scaleplants operated downstream of conventional activated sludge plants. The ozone reactivity of all metabolites(expressed as the ozone dose to remove 90% of the compound/decadic ozone dose) was lower than those oftheir parent compounds. The decadic ozone dose was 1.0, 1.3 and 1.1 mg O3/mg DOC for Epoxy-carbamazepine,Di-OH-carbamazepine and N-Desmethyl tramadol, respectively.20–40% of the remaining metabolites were removed in a polishing sand/BAC-filter (biological activated carbon).Similar removal was observed for Epoxy-carbamazepine, Di-OH-carbamazepine and Hydroxy-diclofenac in aconstructed wetland. However, the sand/anthracite filter had no effect. All four metabolites were removed in aGAC (granulated activated carbon) filter.

The degradation potential of micropollutants and transformation products in biological post-treatment after ozonation is partly unknown. A pilot plant with ozonation and subsequent biological treatment in a moving bed biofilm reactor (MBBR) was thus operated over 16 months to investigate the removal of micropollutants and the formation and removal of N-oxide transformation products. Lab-scale kinetic experiments were performed in parallel. At a moderate ozone dose of 0.5 g O3 g−1 DOC, further degradation of gabapentin and 3 iodinated contrast media (iomeprol, iopamidol, and iohexol) could be induced by the biofilm at prolonged exposure times. To facilitate comparison of feeding regimens in biofilm systems a new surface-related degradation rate constant was introduced. The availability of substrates in the pilot MBBR influenced the micropollutant degradation kinetics with increasing and decreasing degradation rates. N-oxides from erythromycin, clarithromycin, tramadol, and venlafaxine were formed during ozonation and could not be degraded by the biofilm.

The removal of micropollutants from municipal wastewater is challenged by the number of compounds with diverse physico-chemical properties. Ozonation is increasingly used to remove micropollutants from wastewater. However, ozonation does not necessarily result in complete mineralization of the organic micropollutants but rather transforms them into new compounds which could be persistent or have adverse environmental effects. To explore ozone dose dependency of the formation and successive removal of ozonation products, two pilot-scale and one full-scale ozonation plants were operated subsequent to a conventional activated sludge treatment. The results from these trials indicated that the concentrations of several N-oxides, such as Erythromycin N-oxide, Venlafaxine N-oxide and Tramadol N-oxide, increased up to an ozone dose of 0.56–0.61 mg O3/mg DOC while they decreased at elevated doses of 0.7–1.0 mg O3/mg DOC. Similar results were also obtained for two transformation products of Diclofenac (Diclofenac 2,5-quinone imine and 1-(2,6-dichlorophenyl)indolin-2,3-dione) and one transformation product of Carbamazepine (1-(2-benzoic acid)-(1H,3H)-quinazoline-2,4-dione), where the highest concentrations appeared around 0.27–0.31 mg O3/mg DOC. The formation maximum of a given compound occurred at a specific ozone dose that is characteristic for each compound, but seemed to be independent of the wastewater used for the experiments at the two pilots and the full-scale plant.