Multimedia distributions and the fate of microcystins from freshwater discharge in the Geum River Estuary, South Korea: Applicability of POCIS for monitoring of microalgal biotoxins

Abstract

Here, we investigated the characteristics of the environmental multimedia distribution of microcystins (MCs) introduced from freshwater discharge through the estuary dam of the Geum River. In addition, the applicability of a passive sampling device (polar organic chemical integrative sampler, POCIS) for monitoring MCs was evaluated. Surface water, suspended solids (SS), sediments, and oysters were collected from the inner and outer estuary dam. Seven MC variants were analyzed using HPLC-MS/MS. POCIS was deployed at three sites over one week, and MCs were monitored for four weeks from August to September 2019. Before POCIS was deployed in the field, compounds-specific sampling rates of MCs were determined as functions of water temperature (10, 20, and 30 °C), flow rate (0, 0.38, and 0.76 m s−1), and salinity (0, 15, and 30 psu) in the laboratory. The sampling rates of MCs in POCIS increased significantly with increasing water temperature and flow rate, whereas salinity did not significantly affect the sampling rates between freshwater and saltwater. The MCs in the Geum River Estuary mainly existed as particulate forms (mean: 78%), with relatively low proportions of dissolved forms (mean: 22%), indicating that MCs were mainly contained in cyanobacterial cells. There was no significant correlation among the concentrations of MCs in water, SS, sediments, and oysters. Time-weighted average concentrations of MCs from POCIS were not significantly correlated with the concentrations of MCs in water and oysters. The metabolites of MCs, including MC-LR-GSH, MC-LR-Cys, MC-RR-GSH, and MC-RR-Cys, were detected in oysters (no metabolites were detected in POCIS). Overall, POCIS can be useful for monitoring dissolved MCs in the aquatic ecosystem, particularly in calculating time-weighted average concentrations, but it seems to have limitations in evaluating the contamination status of total MCs, mainly in particulate form.