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With the addition of perfluorooctanesulfonate (PFOS), chlordecone, hexachlorocyclohexane (HCH) isomers and endosulfan to the Stockholm Convention, the list of chemicals addressed by the Convention no longer consists solely of hydrophobic organics. Water has become a widely used environmental matrix for monitoring POPs, particularly for the chlorinated pesticides, despite challenges related to collecting samples and determining trace levels. Here we review the sampling and analytical considerations for water sampling of POPs in general, and the hydrophilic POPs in particular, with the goal of identifying and recommending best approaches particularly for assessment of spatial and temporal trends on a global scale. Methods are available for both “active” and “passive” sampling of water for hydrophilic POPs, however, no single approach can be recommended at this time. A performance based approach in which the sampling and quantitative analysis is evaluated is needed so that future global trends of hydrophilic POPs can be monitored.