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... The US EPA method selected six MC congeners to quantitate, but there was little explanation as to why these six were chosen. When reviewing literature in search of LC/MS/MS analyses performed with more than six MC congeners and/or nontargeted analyses throughout the US, results were limited [23][24][25][26][27][28]. Based on US studies, D-Asp 3 MC-LR, D-Asp 3 -RR, Dha 7 -RR, and HtyR are often reported at more than 20% of the total MC concentration [23,24,[29][30][31]. ...
Fast and reliable workflows are needed to quantitate microcystins (MCs), a ubiquitous class of hepatotoxic cyanotoxins, so that the impact of human and environmental exposure is assessed quickly and minimized. Our goal was to develop a high-throughput online concentration liquid chromatography tandem mass spectrometry (LC/MS/MS) workflow to quantitate the 12 commercially available MCs and nodularin in surface and drinking waters. The method run time was 8.5 min with detection limits in the low ng/L range and minimum reporting levels between 5 and 10 ng/L. This workflow was benchmarked by determining the prevalence of MCs and comparing the Adda-ELISA quantitation to our new workflow from 122 samples representing 31 waterbodies throughout Michigan. The frequency of MC occurrence was MC-LA > LR > RR > D-Asp3-LR > YR > HilR > WR > D-Asp3-RR > HtyR > LY = LW = LF, while MC-RR had the highest concentrations. MCs were detected in 33 samples and 13 of these samples had more than 20% of their total MC concentration from MCs not present in US Environmental Protection Agency (US EPA) Method 544. Furthermore, seasonal deviations between the LC/MS/MS and Adda-ELISA data suggest Adda-ELISA cross-reacts with MC degradation products. This workflow provides less than 24-h turnaround for quantification and also identified key differences between LC/MS/MS and ELISA quantitation that should be investigated further.
Midlatitude waterbodies are experiencing increased cyanobacteria blooms that necessitate health advisories to protect waterbody users. Although surface waters may contain cyanotoxins such as microcystin (MC) concentrations that pose potential public health risks, little is known about MC contamination of shoreline sediments. Based on growing evidence that lake and reservoir sediments can accumulate MCs, we hypothesized that shoreline sediments (i.e., recreational beaches) may accumulate MCs and thereby pose a potential health risk to recreational users even if people stay out of contaminated water. We sampled nearshore surface water, shoreline sediment, and porewater from seven Washington State, USA, lakes/reservoirs recreational beaches to determine MC presence/absence during or immediately following cyanobacteria blooms. We found MCs in shoreline sediments at all waterbodies using ELISA and LC-MS/MS. MC concentrations in shoreline sediments and porewaters persisted for 20 days following dissipation of cyanobacteria blooms when MC concentrations were near analytical reporting limits in corresponding surface waters. A human health risk assessment based on potential MC exposure through incidental ingestion of porewaters and sediments found, even when very high MC concentrations occur in surface waters (i.e., >11,000 μg/L), estimated ingestion doses are below MC World Health Organization tolerable daily intake and U.S. Environmental Protection Agency’s risk reference dose. While our findings suggest MCs in Washington State recreational beaches in 2018 did not present a significant human health risk, future blooms with higher MC concentrations could pose human health risks via the shoreline sediment/porewater exposure pathway.
