Direct photodegradation of 36 organic micropollutants under simulated solar radiation: Comparison with free-water surface constructed wetland and influence of chemical structure.

Micropollutants such as pharmaceuticals and pesticides are still found in treated municipal effluent and are discharged into the natural environment. Natural direct photodegradation may be one pathway for removing these micropollutants in treatment processes such as free-water surface constructed wetlands (CW). This work was set out to evaluate the half-life (t1/2) of direct photodegradation of 36 micropollutants under controlled conditions of light exposure close to solar radiation. The results allowed to classify the micropollutants into three groups (fast, medium and slow). Seven micropollutants were classified in the fast group with t1/2 between 0.05 h and 0.79 h, 24 in the medium group with t1/2 between 5.3 h and 49.7 h, and five in the slow group with t1/2 between 56 h and 118 h. The t1/2 values obtained in laboratory were compared with those from a CW receiving treated wastewater. Correction factors were calculated to adjust the in situ data for the light intensity in laboratory and improved the correspondence especially for the micropollutants of the fast and medium groups. Finally, an innovative method based on statistical tests highlighted the chemical functions characteristic of micropollutants sensitive to photodegradation (OH-CË­O, CË­N-O-, =N-OH, -CH=N, -O-PË­O, -CË­C-) and with low sensitivity (-O-R, -Cl).

Removal efficiencies and kinetic rate constants of xenobiotics by ozonation in tertiary treatment.

This study gives a full overview of the chemical oxidation by ozone of selected xenobiotics usually present in effluents of conventional wastewater treatment plants. A qualitative and quantitative overview of literature data was made, and describes the ozonation efficiency and processes for the elimination of 12 xenobiotics (pesticides and pharmaceuticals). A database was built, compiling literature results of experimental ozonation assays in laboratory and real-scale conditions. Special attention was paid to selecting the data and compiling reliable results on removal efficiencies and kinetic parameters. An original study was performed in a semi-batch reactor applying ozone on secondary effluent spiked beforehand with a cocktail of 12 xenobiotics. The results of this study were compared with the literature data to evaluate the influence of the kinetic competition of xenobiotics in spiked wastewater in the determination of kinetic rate constants. These 12 xenobiotics were classified into three groups (high-/medium-/low-oxidizable) according to the ranges of their direct kinetic rate constants (kO3). A best effective ozone dose between 0.2 and 0.4 gO3 gDOC-1 is proposed for the elimination of xenobiotics. The predominant elimination pathway between direct and indirect oxidation was identified for each xenobiotic.

A review of the photodegradability and transformation products of 13 pharmaceuticals and pesticides relevant to sewage polishing treatment.

Many xenobiotics are only partially treated by conventional wastewater treatment plants. Photodegradation is one promising solution currently being investigated to improve their removal from effluents. We present an in-depth review of the photodegradation kinetic parameters of selected pesticides and pharmaceuticals and assess whether the data available in the literature are applicable to polishing treatment processes under sunlight. We made a thorough inventory of literature data describing the photodegradation of pesticides and pharmaceuticals in water, the laboratory, pilot plants, and in situ conditions. To this end, we built a database compiling results on photodegradation experiments from 70 scientific publications covering 13 xenobiotics commonly found in secondary effluents. Special care was taken to compile reliable data on photolysis kinetic parameters (half-life and kinetic rate constant) and removal efficiencies. We also include a comprehensive description of experimental operating conditions and an up-to-date inventory of known phototransformation products. As practical outputs we (i) propose a classification for the xenobiotics according to their photodegradability: fast-, medium- and slow-photodegradable, (ii) compare kinetic parameters in direct and indirect photodegradation conditions, and (iii) list 140 phototransformation products formed by direct or indirect photodegradation. We conclude by identifying gaps in the literature that need to be filled to adapt these available results to the conditions of polishing processes.