Abteilung Wasserressourcen und Trinkwasser

In response to water scarcity and an increased recognition of the risks associated with the presence of chemical contaminants, environmental engineers have developed advanced water treatment systems that are capable of converting municipal wastewater effluent into drinking water. This practice, which is referred to as potable water reuse, typically relies upon reverse osmosis (RO) treatment followed by exposure to ultraviolet (UV) light and addition of hydrogen peroxide (H₂O₂). These two treatment processes individually are capable of controlling many of the chemical and microbial contaminants in wastewater; however, a few chemicals may still be present after treatment at concentrations that affect water quality.
Low-molecular weight (<200 Da), uncharged compounds represent the greatest challenge for RO treatment. For potable water reuse systems, compounds of greatest concern include oxidation products formed during treatment (e.g., N-nitrosodimethylamine, halogenated disinfection byproducts) and compounds present in wastewater effluent (e.g., odorous compounds, organic solvents). Although the concentrations of most of these compounds decrease to levels where they no longer compromise water quality after they encounter the second treatment barrier (i.e., UV/H₂O₂), low-molecular weight compounds that are resistant to direct photolysis and exhibit low reactivity with hydroxyl radical (·OH) may persist. While attempts to identify the compounds that pass through both barriers have accounted for approximately half of the dissolved organic carbon remaining after treatment, it is unlikely that a significant fraction of the remaining unknowns will ever be identified with current analytical techniques. Nonetheless, the toxicity-weighted concentration of certain known compounds (e.g., disinfection byproducts) is typically lower in RO-UV/H₂O₂ treated water than conventional drinking water.
To avoid the expense associated with managing the concentrate produced by RO, environmental engineers have begun to employ alternative treatment barriers. The use of alternatives such as nanofiltration, ozonation followed by biological filtration, or activated carbon filtration avoids the problems associated with the production and disposal of RO concentrate, but they may allow a larger number of chemical contaminants to pass through the treatment process. In addition to the transformation products and solvents that pose risks in the RO-UV/H₂O₂ system, these alternative barriers are challenged by larger, polar compounds that are not amenable to oxidation, such as perfluoroalkyl acids and phosphate-containing flame retardants.
To fully protect consumers who rely upon potable water reuse systems, new policies are needed to prevent chemicals that are difficult to remove during advanced treatment from entering the sewer system. By using knowledge about the composition of municipal wastewater and the mechanisms through which contaminants are removed during treatment, it should be possible to safely reuse municipal wastewater effluent as a drinking water source.

The abatement of organic micropollutants during oxidation processes has become an emerging issue for various urban water systems such as drinking water, wastewater, and water reuse. Reaction kinetics and mechanisms play an important role in terms of efficiency of these processes and the formation of transformation products, which are controlled by functional groups in the micropollutants and the applied oxidants. So far, the kinetic and mechanistic information on the underlying reactions was obtained by experimental studies; additionally, predictive quantitative structure–activity relationships (QSARs) were applied to determine reaction kinetics for the oxidation of emerging compounds. Since this experimental approach is very laborious and there are tens of thousands potential contaminants, alternative strategies need to be developed to predict the fate of micropollutants during oxidative water treatment. Due to significant developments in quantum chemical (QC) computations in recent years and increased computational capacity, QC-based methods have become an alternative or a supplement to the current experimental approach.
This Account provides a critical assessment of the current state-of-the-art of QC-based methods for the assessment of oxidation of micropollutants. Starting from a given input structure, QC computations need to locate energetic minima on the potential energy surface (PES). Then, useful thermodynamic and kinetic information can be estimated by different approaches: Experimentally determined reaction mechanisms can be validated by identification of transition structures on the PES, which can be obtained for addition reactions, heavy atom transfer (Cl⁺, Br⁺, O·) and H atom transfer (simultaneous proton and electron transfer) reactions. However, transition structures in the PES cannot be obtained for e^–-transfer reactions.
Second-order rate constants k for the reactions of micropollutants with chemical oxidants can be obtained by ab initio calculations or by QSARs with various QC descriptors. It has been demonstrated that second-order rate constants from ab initio calculations are within factors 3–750 of the measured values, whereas QSAR-based methods can achieve factors 2–4 compared to the experimental data. The orbital eigenvalue of the highest occupied molecular orbital (E_HOMO) is the most commonly used descriptor for QSAR-based computations of k-values.
In combination with results from experimental studies, QC computations can also be applied to investigate reaction mechanisms for verification/understanding of oxidative mechanisms, calculation of branching ratios or regioselectivity, evaluation of the experimental product distribution and assessment of substitution effects. Furthermore, other important physical-chemical constants such as unknown equilibria for species, which are not measurable due to low concentrations, or pK_a values of reactive transient species can be estimated. With further development of QC-based methods, it will become possible to implement kinetic and mechanistic information from such computations in in silico models to predict oxidative transformation of micropollutants. Such predictions can then be complemented by tailored experimental studies to confirm/falsify the computations.

Aliphatic amines are common constituents in micropollutants and dissolved organic matter and present in elevated concentrations in wastewater-impacted source waters. Due to high reactivity, reactions of aliphatic amines with ozone are likely to occur during ozonation in water and wastewater treatment. We investigated the kinetics and mechanisms of the reactions of ozone with ethylamine, diethylamine, and triethylamine as model nitrogenous compounds. Species-specific second-order rate constants for the neutral parent amines ranged from 9.3 × 10⁴ to 2.2 × 10⁶ M⁻¹s⁻¹ and the apparent second-order rate constants at pH 7 for potential or identified transformation products were 6.8 × 10⁵ M⁻¹s⁻¹ for N,N-diethylhydroxylamine, ∼10⁵ M⁻¹s⁻¹ for N-ethylhydroxylamine, 1.9 × 10³ M⁻¹s⁻¹ for N-ethylethanimine oxide, and 3.4 M⁻¹s⁻¹ for nitroethane. Product analyses revealed that all amines were transformed to products containing a nitrogen-oxygen bond (e.g., triethylamine N-oxide and nitroethane) with high yields, i.e., 64–100% with regard to the abated target amines. These findings could be confirmed by measurements of singlet oxygen and hydroxyl radical which are formed during the amine-ozone reactions. Based on the high yields of nitroethane from ethylamine and diethylamine, a significant formation of nitroalkanes can be expected during ozonation of waters containing high levels of dissolved organic nitrogen, as expected in wastewaters or wastewater-impaired source waters. This may pose adverse effects on the aquatic environment and human health.