Photodegradation of cyanotoxins in surface waters.

Cyanotoxin-producing harmful algal blooms (HABs) are a global occurrence and pose ecotoxicological threats to humans and animals alike. The presence of cyanotoxins can seriously harm or kill nearby wildlife and restrict a body of water's use as a drinking water supply and recreational site, making it imperative to fully understand their fate and transport in natural waters. Photodegradation contributes to the overall degradation of cyanotoxins in environmental systems, especially for those present in the photic zone of surface waters. This makes photochemical transformation mechanisms important factors to account for when assessing the persistence of cyanotoxins in environmental systems. This paper reviews current knowledge on the photodegradation rates and pathways of cyanotoxins that can occur over the course of HABs. Sensitized, or indirect, photolysis contributes to the degradation of all cyanotoxins addressed in this paper (anatoxins, cylindrospermopsins, domoic acids, microcystins, and nodularins), with hydroxyl radicals (•OH), excited triplet states formed from the absorption of light by dissolved organic matter (3DOM*), and photosynthetic pigment sensitized pathways being of primary interest. Direct photolysis pathways play a less significant role, but are still relevant for most of the cyanotoxins discussed in this paper.

Effects of Ozone on the Photochemical and Photophysical Properties of Dissolved Organic Matter.

This study focused on the effects of ozonation on the photochemical and photophysical properties of dissolved organic matter (DOM). Upon ozonation, a decrease in DOM absorbance was observed in parallel with an increase in singlet oxygen (1O2) and fluorescence quantum yields (Φ1O2 and ΦF). The increase in Φ1O2 was attributed to the formation of quinone-like moieties during ozonation of the phenolic moieties of DOM, while the increase in ΦF can be explained by a significant decrease in the internal conversion rate of the first excited singlet state of the DOM (1DOM*). It is a consequence of an increase in the average energy of the first electronic transition (S1 → S0) that was assessed using the wavelength of maximum fluorescence emission (λF,max). Furthermore, ozonation did not affect the ratio of the apparent steady-state concentrations of excited triplet DOM (3DOM*) and 1O2, indicating that ozonation does not affect the efficiency of 1O2 production from 3DOM*. The consequences of these changes for the phototransformation rates of micropollutants in surface waters were examined using photochemical model calculations. The decrease in DOM absorbance caused by ozonation leads to an enhancement of direct photolysis rates due to the increased transparency of the water. Rates of indirect photooxidation induced by 1O2 and 3DOM* slightly decrease after ozonation.