RESUMO
A series of ten photolysis experiments was conducted with sediments exposed to Microcystis sp. blooms to determine if sunlight is capable of mobilizing the biotoxin microcystin-LR (MC-LR) into the water column. There was a net photorelease of MC-LR in irradiated suspensions in all cases relative to dark controls, ranging from 0.4 to 192µgL-1g-1 into the dissolved phase. This should be viewed as a minimum estimate of photorelease due to concurrent photodegradation of dissolved toxin. Dissolved MC-LR concentrations in a sediment suspension increased linearly in the aqueous phase during a six-hour irradiation with simulated sunlight suggesting that longer exposure times produce greater quantities of MC-LR. There was a significant positive correlation between photorelease of toxin and percent organic carbon of the resuspended material, implying that organic-rich sediments yield the greatest photorelease of MC-LR upon exposure to full spectrum sunlight. Samples exposed to photosynthetically active radiation (400nm-700nm) were responsible for less than 2% of the photorelease compared to full spectrum exposures. Model calculations indicate that photochemical processing of bloom impacted sediments could be responsible for as much as 100% of the average standing stock of MC-LR in a freshwater pond located in southeastern North Carolina, where surface water concentrations were also measured. Mass spectrometric analysis revealed a new peak in light exposed flasks that appears to be a photo-induced isomerized product of MC-LR. Photoproduction from resuspended sediments therefore represents a significant but previously unrecognized source of highly toxic MC-LR and photoproducts of unknown toxicity and fate to aquatic ecosystems.