Assessment of the roles of reactive oxygen species in the UV and visible light photocatalytic degradation of cyanotoxins and water taste and odor compounds using C-TiO2.

Visible light (VIS) photocatalysis has large potential as a sustainable water treatment process, however the reaction pathways and degradation processes of organic pollutants are not yet clearly defined. The presence of cyanobacteria cause water quality problems since several genera can produce potent cyanotoxins, harmful to human health. In addition, cyanobacteria produce taste and odor compounds, which pose serious aesthetic problems in drinking water. Although photocatalytic degradation of cyanotoxins and taste and odor compounds have been reported under UV-A light in the presence of TiO2, limited studies have been reported on their degradation pathways by VIS photocatalysis of these problematic compounds. The main objectives of this work were to study the VIS photocatalytic degradation process, define the reactive oxygen species (ROS) involved and elucidate the reaction mechanisms. We report carbon doped TiO2 (C-TiO2) under VIS leads to the slow degradation of cyanotoxins, microcystin-LR (MC-LR) and cylindrospermopsin (CYN), while taste and odor compounds, geosmin and 2-methylisoborneol, were not appreciably degraded. Further studies were carried-out employing several specific radical scavengers (potassium bromide, isopropyl alcohol, sodium azide, superoxide dismutase and catalase) and probes (coumarin) to assess the role of different ROS (hydroxyl radical OH, singlet oxygen (1)O2, superoxide radical anion [Formula: see text] ) in the degradation processes. Reaction pathways of MC-LR and CYN were defined through identification and monitoring of intermediates using liquid chromatography tandem mass spectrometry (LC-MS/MS) for VIS in comparison with UV-A photocatalytic treatment. The effects of scavengers and probes on the degradation process under VIS, as well as the differences in product distributions under VIS and UV-A, suggested that the main species in VIS photocatalysis is [Formula: see text] , with OH and (1)O2 playing minor roles in the degradation.

Photocatalytic degradation of cylindrospermopsin under UV-A, solar and visible light using TiO2. Mineralization and intermediate products.

Cyanobacteria (blue-green algae) are considered an important water quality problem, since several genera can produce toxins, called cyanotoxins that are harmful to human health. Cylindrospermopsin (CYN) is an alkaloid-like potent cyanotoxin that has been reported in water reservoirs and lakes worldwide. In this paper the removal of CYN from water by UV-A, solar and visible light photocatalysis was investigated. Two different commercially available TiO2 photocatalysts were used, i.e., Degussa P25 and Kronos-vlp7000. Complete degradation of CYN was achieved with both photocatalysts in 15 and 40 min under UV-A and 40 and 120 min under solar light irradiation, for Degussa P25 and Kronos vlp-7000 respectively. Experiments in the absence of photocatalysts showed that direct photolysis was negligible. Under visible light irradiation only the Kronos vlp-7000 which is a visible light activated catalyst was able to degrade CYN. A number of intermediates were identified and a complete degradation pathway is proposed, leading to the conclusion that hydroxyl radical attack is the main mechanism followed. TOC and inorganic ions (NO2-, NO3-, SO4(2-) and NH4+) determinations suggested that complete mineralization of CYN was achieved under UV-A in the presence of Degussa P25.

Determination of microcystins and nodularin (cyanobacterial toxins) in water by LC-MS/MS. Monitoring of Lake Marathonas, a water reservoir of Athens, Greece.

A method for the determination of the hepatotoxic cyanotoxins microcystins (MCs, i.e. MC-LR, MC-RR, MC-YR, MC-LA) and nodularin (NOD) in water was developed using liquid chromatography with electrospray ionization triple quadrupole mass spectrometry (LC-ESI-MS/MS) after solid phase extraction (SPE). New patterns of fragmentation of MC-LA were observed under the experimental conditions used. The method was fully validated to meet accreditation criteria. Mean recoveries at three concentration levels (0.006, 0.1 and 1 µg L(-1)) ranged between 70 and 114% with %RSD values generally below 20%. Detection limits were 2 ng L(-1) for all hepatotoxins. The method was applied to study the occurrence of MCs and NOD in Lake Marathonas, a water reservoir of Athens, over a period from July 2007 to December 2010. The protein phosphatase inhibition assay (PPIA) was additionally used for fast screening of samples. MC-YR, MC-LR and MC-RR were detected and found to vary seasonally with consistent peaks during early autumn, having maximum concentrations of 717, 451 and 174 ng L(-1), respectively. The results of this study constitute the first report on the presence, concentration levels and seasonal variations of MCs in Lake Marathonas. None of the target cyanotoxins were detected in treated drinking water samples during the period of the study.