Groundwater Pollution by Perfluorinated Surfactants in Tokyo

Perfluorinated surfactants (PFSs) in groundwater were analyzed to reveal their distribution and sources. Sixteen groundwater and spring samples were collected from the Tokyo metropolitan area, and nine PFSs, including perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA), were analyzed by liquid chromatography−tandem mass spectrometry. A column test using artificial street runoff was also performed to study their behavior. PFSs were detected in all groundwater samples, some at concentrations comparable to those in wastewater and street runoff, suggesting widespread contamination of groundwater by PFSs. In particular, PFOS was more abundant in groundwater than in rivers, wastewater, and street runoff. This was attributed to its production from the degradation of its precursors, as supported by the column test. The occurrence of short-chain perfluorocarboxylates (PFCAs) in groundwater was also consistent with the results of the column test, showing that limited amounts of short-chain PFCAs were removed by soil, as the efficiency of removal increased with the chain length. We evaluated the contributions of PFCAs from wastewater and surface runoff to groundwater by using two indicators, the long/(short + long) ratio and the even/(even + odd) ratio. Both ratios showed good agreement in their calculated contributions in heavily contaminated groundwater where breakthroughs likely occurred. Wastewater and surface runoff contributed to 54−86% and 16−46% of PFCAs, respectively, in groundwater.