Evaluation of the efficiency of cyclodextrin polymers as sustainable sampling material for catching palytoxin-like compounds in seawater

Abstract

Palytoxin-like compounds, including ovatoxins, are potent emerging toxins responsible for human respiratory poisonings following inhalation of contaminated marine aerosols. Periodic massive proliferations of the ovatoxin-producing organism (Ostreopsis cf. ovata) worldwide, particularly in the Mediterranean, have caused severe toxic outbreaks, drawing the attention of health authorities. At present, an efficient and sustainable sampling system for monitoring ovatoxins in seawater remains unavailable. Herein, different cyclodextrin (CD) polymers were investigated as a green and effective alternative to conventional and low-performing resins to detect ovatoxins in seawater. Spiking experiments using different concentrations of palytoxin or ovatoxins (namely 200 and 3.3 ng PLTX/mL or 200 ng OVTX-a/mL) were conducted and LC-HRMS was used to evaluate the suitability of CD polymers in capturing palytoxin-like compounds. Several conditions were tested for extracting polymer materials, including different extraction times (1.5 to 4 h), various solvent mixtures (acidic or alkaline), and organic modifiers (methanol or acetonitrile) at different ratios. Among the tested polymers, γ-CD-hexamethylene diisocyanate (HDI) resulted to be the most promising one, providing ovatoxin recoveries in the range 82–108% at a spiking level of 200 ng OVTX-a per mL. The best extracting condition was alkaline pH methanol:water 8:2 mixture, which showed the best palytoxin recovery in both high and low concentration spiking experiments. Finally, a time-dependent increase in the amount of ovatoxins captured by γ-CD-HDI disks deployed in O. cf. ovata cultures was observed. These findings provide valuable insights on the efficiency of passive sampling using CD polymers for capturing ovatoxins during O. cf. ovata bloom events.