Heterogeneous photocatalytic degradation of pharmaceuticals in synthetic and real matrices using a tube-in-tube membrane reactor with radial addition of H2O2.

A tube-in-tube membrane reactor, with radial addition of hydrogen peroxide, was used for the oxidation of four pharmaceuticals, paracetamol (PCT), furosemide (FRS), nimesulide (NMD), and diazepam (DZP), in a continuous-mode operation, using photochemical and photocatalytic processes, driven by UVA or UVC photons. This reactor allows a controlled titration of small H2O2 doses (inside-out mode) to the catalyst particles immobilized in the membrane shell side and to the annular space between the membrane inner tubing and the concentric outer quartz tubing, where water to be treated flows. Tests were performed using synthetic (SWW) and real (urban wastewater after secondary treatment) (UWW) matrices, both spiked with the pharmaceutical mix solution (200 µg L-1 of each). The photochemical and photocatalytic oxidation efficiency was evaluated as a function of H2O2 dose (5-20 mg L-1), oxidant injection mode (radial permeation vs injection upstream from the reactor inlet), light source (UVA vs UVC lamps) and aqueous matrix (synthetic vs real matrix). At steady-state regime, the UVC/H2O2/TiO2 system, with radial H2O2 addition (20 mg L-1), showed the highest pharmaceuticals removal percentage, PCT (27.4%), FRS (35.0%), NMD (24.2%) and DZP (30.0%) in SWW. A substantial decrease in pharmaceuticals elimination was observed for UWW (PCT - 11.5%, FRS - 20.3%, NMD - 8.2% and DZP - 12.6%), in comparison with the SWW matrix. Finally, twelve transformation products (TPs) were identified; most of them showed in their structures hydroxylation in aromatic moiety; all TPs chemical structures were evaluated by BIOWIN software indicating that the TPs are non-biodegradables.

Investigation of pharmaceuticals and their metabolites in Brazilian hospital wastewater by LC-QTOF MS screening combined with a preliminary exposure and in silico risk assessment.

This work evaluates the occurrence of pharmaceuticals, with special emphasis on their metabolites, in raw hospital wastewater (HWW) using wide-scope screening based on liquid chromatography coupled to high resolution mass spectrometry. The applied strategy uses an extended purpose-built database, containing >1000 pharmaceuticals and 250 metabolites. Raw HWW samples from a hospital located in south Brazil were collected over six months, with a monthly sampling frequency. Accurate-mass full-spectrum data provided by quadrupole-time of flight MS allowed the identification of 43 pharmaceuticals and up to 31 metabolites in the samples under study. Additionally, other four metabolites not included in the initial database could be identified using a complementary strategy based on the common fragmentation pathway between the parent compound and its metabolites. Nine metabolites derived from four pharmaceuticals were identified in the raw HWW samples, whereas their parent compounds were not found in these samples. The results of this work illustrate the importance of including not only parent pharmaceuticals but also their main metabolites in screening analysis. Besides, the inclusion of in silico QSAR predictions allowed assessing the environmental fate and effect of pharmaceuticals and metabolites in terms of biodegradability, as possible Persistent, Bioaccumulative and Toxic (PBT) compounds, and their potential hazard to the aquatic environment.

Degradation of pharmaceuticals in different water matrices by a solar homo/heterogeneous photo-Fenton process over modified alginate spheres.

A solar homo/heterogeneous photo-Fenton process using five materials (Fe(II), Fe(III), mining waste, Fe(II)/mining waste, and Fe(III)/mining waste) supported on sodium alginate was used as a strategy to iron dosage for the degradation of eight pharmaceuticals in three different water matrices (distilled water, simulated wastewater, and hospital wastewater). Experiments were carried out in a photoreactor with a capacity of 1 L, using 3 g of iron-alginate spheres and an initial hydrogen peroxide concentration of 25 mg L-1, at pH 5.0. All the materials prepared were characterized by different techniques. The Fe(III)-alginate spheres presented the best pharmaceutical degradation after a treatment time of 116 min. Nineteen transformation products generated during the solar photo-Fenton process were identified by liquid chromatography coupled to quadrupole time-of-flight mass spectrometry, using a purpose-built database developed for detecting these transformation products. Finally, the transformation products identified were classified according to their toxicity and predicted biodegradability.

Degradation and ecotoxicity of dye Reactive Black 5 after reductive-oxidative process : Environmental Science and Pollution Research.

This research paper describes the study of a reduction-oxidation system using commercial steel wool (Fe0) and H2O2 for degradation of the dye Reactive Black 5 and aromatic compounds in water. The reductive process alone allowed the almost complete removal of color (97 ± 1 %) after 60 min of reaction. The decrease in spectral area (λ = 599 nm) associated with the chromophore group indicates breakage of the azo bonds. Moreover, the significant change in UV spectra can be associated with the formation of aromatic amines. Regarding the transformation products, a spectrophotometric method based on the diazotization reaction was employed to identify aromatic amines after reductive process, using sulfanilic acid as a model of aromatic amines. In addition, association with Fenton reagents improved the efficiency in the system with 93 ± 1 % degradation of intermediates formed during the reductive process. Ecotoxicological analysis revealed that the dye solution, after the reductive and oxidative processes, was not toxic to Lactuca sativa seeds. For Daphnia magna, the EC50 (%) values observed revealed that dye solution has an EC50(%) = 74.1 and after reductive process, the toxicity increased (EC50(%) = 63.5), which might be related to the formation of aromatic amines. However, after the Fenton process, the EC50 (%) was >100. These results demonstrated that the Fenton reaction using steel wool as an iron source was very efficient to decrease color, aromatic transformation products, and the ecotoxicity of Reactive Black 5 in solution.