Photocatalytic degradation of selected anticancer drugs and identification of their transformation products in water by liquid chromatography-high resolution mass spectrometry.

A study on the fate of two antineoplastic drugs, methotrexate and doxorubicin, in the aquatic environment is presented. The investigation involved a study of their decomposition under dark experiments, homogeneous photolysis and heterogeneous photocatalysis using titanium dioxide, the identification of intermediate compounds, as well as the assessment of acute toxicity over time. The analysis were carried out using LC (ESI positive mode) coupled with LTQ-Orbitrap analyser; accurate mass-to-charge ratios of parent ions were reported with inaccuracy below 10mmu, which guarantee the correct assignment of their molecular formula in all cases, while their MS(2) and MS(3) spectra showed several structural-diagnostic ions that allowed to characterize the different transformation products and to discriminate the isobaric species. Fourteen and eight main species were identified subsequently to doxorubicin or methotrexate transformation. The major transformation processes for doxorubicin involved (poli)hydroxylation and/or oxidation of the molecule, or the detachment of the sugar moiety. Methotrexate transformation involved decarboxylation or the molecule cleavage. Acute toxicity measurements showed that not only the two drugs exhibit high toxicity, but also their initial transformation products are highly toxic.

Application of semipermeable membrane device for assessing toxicity in drinking water.

Semipermeable membrane devices (SPMDs) mimic passive diffusive transport of bioavailable hydrophobic organic compounds through biological membranes and their partitioning between lipids and environmental levels. Our study was developed on a surface water treatment plant based in Turin, Northern Italy. The investigated plant treats Po River surface water and it supplies about 20% of the drinking water required by Turin city (about one million inhabitants). Surface water (input) and drinking water (output) were monitored with SPMDs from October 2001 to January 2004, over a period of 30 days. The contaminant residues, monthly extracted from SPMDs by dialysis in organic solvent, were tested with the Microtox acute toxic test and with the Ames mutagenicity test. Same extracts were also analyzed with gas chromatography--mass spectrometry technique in order to characterise the organic pollutants sampled, especially Polycyclic Aromatic Hydrocarbons (PAHs). Although the PAHs mean concentration is about one hundred times lower in the output samples, the mean toxic units are similar in drinking and surface water. Our data indicate that the SPMD is a suitable tool to assess the possible toxicity in drinking water.

Abatement of waste-water biorefractory organics via electro-oxidative treatment.

The electrochemical oxidation of coumaric acid, a biorefractory compound present in several industrial waste waters, has been investigated by use of Pt-Ti anodes and at electrolyte concentration (0.02 N NaCl or Na2SO4) low enough to allow direct dischargeability of the waste water into superficial water basins according to the Italian law (DL 152/11-5-99). Particularly, the role of the electrolyte over the conversion rate has been assessed. The obtained results show that the oxidation process should take place both at the electrode surface and in the bulk of the solution, via electrochemically-generated oxidising species (H2O2, persulfates, Cl2, NaClO). The faster coumaric acid abatement rates were found with chloride based electrolytes, which, however, lead to the formation of non-biodegradable small-molecular-weight chlorinated hydrocarbons.