Abstract
Single cell-inductively coupled plasma-mass spectrometry (SC-ICP-MS) is an emerging technology. In this work, we have developed a novel SC-ICP-MS method to quantify metal ions in individual cells of a toxic cyanobacterial species, Microcystis aeruginosa (M. aeruginosa), without complicated post-dosing sample preparation, and applied this method to study the treatment effectiveness of copper-based algaecides (cupric sulfate and EarthTec®) on the toxic algae M. aeruginosa. The developed SC-ICP-MS method uses new intrinsic metal element magnesium to determine real transport efficiency and cell concentration. The cell viability and microcystin-LR release by algaecide treatment were studied by flow cytometry and ultra-fast liquid chromatography-tandem mass spectrometry, respectively. The results showed that this novel method was very rapid, highly sensitive (detection limits of intracellular copper and magnesium were 65 ag/cell and 98 ag/cell, respectively), and reproducible (relative standard deviation within 12%). The algaecide effectiveness study further demonstrated that copper in the forms of cupric sulfate and copper-based algaecide EarthTec® successfully diminished M. aeruginosa populations. The higher the copper concentration used to treat the cells, the faster the speeds of copper uptake and cell lysis in the copper concentrations ranged from 0 to 200 μg/L of copper-based algaecide. The cells exhibit obvious heterogeneity in copper uptake. The result suggests that M. aeruginosa cells uptake and cumulate copper followed by cellular lysis and microcystin-LR release. These novel results indicated that though the copper-based algaecides could control this type of harmful algal bloom, further treatment to remove the released algal toxin from the treated water would be needed.Graphical abstract
Highlights
Harmful algal blooms (HABs) present a complex environmental challenge exacerbated by excessive nitrogen and phosphorus content in aquatic systems associated with agriculture practices [1] and climate change [2]
transport efficiency (TE) refers to the ratio of analyte entering the plasma to the amount of analyte aspirated [45], and represents a key parameter for cell concentration quantification by Single cell (SC)-inductively coupled plasma-mass spectrometry (ICP-MS)
Unlike SP-ICP-MS in which the particle integrity is maintained throughout the nebulization process, many cell types are prone to lysis during sample introduction
Summary
Harmful algal blooms (HABs) present a complex environmental challenge exacerbated by excessive nitrogen and phosphorus content in aquatic systems associated with agriculture practices [1] and climate change [2]. Interventions that have been suggested for Microcystis blooms have spanned mechanical, chemical, biological, genetic, and environmental approaches [9]. Chemical methods have variously employed chemical reagents, such as copperbased algaecides [16,17,18], sodium percarbonate [19], sterol surfactants, sodium hypochlorite, and magnesium hydroxide, to control Microcystis blooms [20]. Among these interventional strategies, the use of cupric sulfate as an algaecide has advanced as an inexpensive and effective solution [18]
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