Leibniz Institute for Baltic Sea Research Warnemünde, Department of Marine Chemistry, Seestraße 15, 18119, Rostock, Germany.
Leibniz Institute for Baltic Sea Research Warnemünde, Department of Marine Chemistry, Seestraße 15, 18119, Rostock, Germany.
Chemosphere. 2021 Jan;262:128327. doi: 10.1016/j.chemosphere.2020.128327. Epub 2020 Sep 16.
The globally used herbicide glyphosate and its metabolite aminomethylphosphonic acid (AMPA) have not yet been reported to occur in the marine environment, presumably due to a lack of suitable analytical methods. In this study, we developed two new methods for the analysis of glyphosate and AMPA in seawater: a small-scale method, which includes an SPE cleanup step that minimizes salt-matrix effects during LC-MS/MS analysis, and a large-scale method that employs an additional SPE preconcentration step. Different SPE materials were evaluated for their suitability to enrich glyphosate and AMPA from saltwater and a molecularly imprinted polymer was selected. Both methods were validated in ultrapure water and environmental seawater. Achieved limits of detection with the small-scale method were 6 and 8 ng/L for glyphosate and AMPA, while the large-scale method achieved 0.12 and 0.22 ng/L, respectively. The small-scale method was used to analyze environmental samples from the Warnow Estuary in Germany. Glyphosate and AMPA could be successfully detected in the samples, but could not be measured beyond the saline estuary due to dilution and degradation effects. A set of samples from the western Baltic Sea was analyzed with the large-scale method. Glyphosate and AMPA could be detected in all Baltic Sea samples, especially at stations close to estuaries. To the best of our knowledge, this is the first report on the occurrence of glyphosate and AMPA in seawater.
全球使用的除草剂草甘膦及其代谢物氨甲基膦酸（AMPA）尚未在海洋环境中报道，据推测这是由于缺乏合适的分析方法。在这项研究中，我们开发了两种新的海水草甘膦和 AMPA 分析方法：一种小规模方法，包括 SPE 净化步骤，可最大程度地减少 LC-MS/MS 分析过程中的盐基质效应；另一种大规模方法，采用额外的 SPE 预浓缩步骤。评估了不同的 SPE 材料，以确定其从咸水中富集草甘膦和 AMPA 的适用性，并选择了一种分子印迹聚合物。这两种方法均在超纯水和环境海水中进行了验证。小规模方法的检出限分别为草甘膦和 AMPA 的 6 和 8 ng/L，而大规模方法的检出限分别为 0.12 和 0.22 ng/L。该小规模方法用于分析来自德国 Warnow 河口的环境样品。在样品中成功检测到草甘膦和 AMPA，但由于稀释和降解作用，在盐水河口之外无法进行测量。还使用大规模方法分析了来自波罗的海西部的一组样品。在所有波罗的海样品中都可以检测到草甘膦和 AMPA，尤其是在靠近河口的站位。据我们所知，这是关于草甘膦和 AMPA 在海水中出现的首次报道。
