BTXs removals by modified clay during mitigation of Karenia brevis bloom: Insights from adsorption and transformation

Abstract

Harmful algal blooms (HABs), especially those caused by toxic dinoflagellates, are spreading in marine ecosystems worldwide. Notably, the prevalence of Karenia brevis blooms and potent brevetoxins (BTXs) pose a serious risk to public health and marine ecosystems. Therefore, developing an environmentally friendly method to effectively control HABs and associated BTXs has been the focus of increasing attention. As a promising method, modified clay (MC) application could effectively control HABs. However, the environmental fate of BTXs during MC treatment has not been fully investigated. For the first time, this study revealed the effect and mechanism of BTX removal by MC from the perspective of adsorption and transformation. The results indicated that polyaluminium chloride-modified clay (PAC-MC, a typical kind of MC) performed well in the adsorption of BTX2 due to the elevated surface potential and more binding sites. The adsorption process was a spontaneous endothermic process that conformed to pseudo-second-order adsorption kinetics (k2 = 6.8 × 10−4, PAC-MC = 0.20 g L−1) and the Freundlich isotherm (Kf = 55.30, 20 °C). In addition, detailed product analysis using liquid chromatography−mass spectrometry/mass spectrometry (LC−MS/MS) indicated that PAC-MC treatment effectively removed the BTX2 and BTX3, especially those in the particulate forms. Surprisingly, PAC-MC could promote the transformation of BTX2 to derivatives, including OR-BTX2, OR-BTX3, and OR-BTX-B5, which were proven to have lower cytotoxicity.