College of Environmental Science and Engineering, Sino-Canada Joint R&D Centre for Water and Environmental Safety, Nankai University, Tianjin 300071, China; Marine Bioresource and Environment Research Center, Key Laboratory of Marine Eco-Environmental Science and Technology, The First Institute of Oceanography, Ministry of Natural Resources, Qingdao 266061, China.
College of Environmental Science and Engineering, Sino-Canada Joint R&D Centre for Water and Environmental Safety, Nankai University, Tianjin 300071, China.
Sci Total Environ. 2022 Dec 20;853:158545. doi: 10.1016/j.scitotenv.2022.158545. Epub 2022 Sep 6.
Hydrophilic cyanotoxins (HCTs), such as paralytic shellfish toxins (PSTs), anatoxin-a (ATX-a), and cylindrospermopsin (CYN) are highly toxic and toxin-producing algae are widely distributed worldwide. However, HCTs, especially PSTs, are rarely reported in freshwater due to analytical limitations. This may result in an underestimation of the ecological risks and health risks. This study developed a new method to detect ATX-a, CYN, and thirteen common PSTs in freshwater simultaneously by using off-line solid phase extraction (SPE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS). The limits of detection (LODs) of all targets were lower than 0.05 μg/L, which could meet the regulatory requirements for monitoring of HCTs in drinking water in different countries and regions. To improve the detection sensitivities for trace PSTs, a method based on off-line SPE and on-line SPE-LC-MS/MS was established with LOD around 0.001 μg/L. GTX1&4, GTX2&3, and GTX5 were detected in freshwater in China for the first time, highlighting that overall communities are facing potential risks of exposure to various PSTs in China. High concentrations of ATX-a and CYN were also detected in freshwater from Northern China. The proposed method helps to understand the pollution status of HCT in water bodies, especially during the non-algal bloom period.
亲水性蓝藻毒素（HCTs），如麻痹性贝类毒素（PSTs）、石房蛤毒素（ATX-a）和鱼腥藻毒素（CYN），具有高度毒性，产毒藻类在全球范围内广泛分布。然而，由于分析上的限制，淡水环境中很少报道 HCTs，尤其是 PSTs。这可能导致对生态风险和健康风险的低估。本研究开发了一种新的方法，通过离线固相萃取（SPE）和液相色谱-串联质谱（LC-MS/MS）同时检测淡水环境中的 ATX-a、CYN 和十三种常见 PSTs。所有目标物的检测限（LODs）均低于 0.05μg/L，可满足不同国家和地区饮用水中 HCTs 监测的监管要求。为了提高痕量 PSTs 的检测灵敏度，建立了一种基于离线 SPE 和在线 SPE-LC-MS/MS 的方法，LOD 约为 0.001μg/L。首次在中国的淡水中检测到 GTX1&4、GTX2&3 和 GTX5，这突显了中国整体社区面临着接触各种 PSTs 的潜在风险。在中国北方的淡水中也检测到了高浓度的 ATX-a 和 CYN。该方法有助于了解水体中 HCT 的污染状况，特别是在非藻类繁殖期。
