Quantification and stability assessment of 7,9-di‑tert‑butyl‑1-oxaspiro(4,5)deca-6,9-diene-2,8‑dione leaching from cross-linked polyethylene pipes using gas and liquid chromatography

This study assesses the formation and stability of the water contaminant 7,9-di‑tert‑butyl‑1-oxaspiro(4,5)deca-6,9-diene-2,8‑dione ([1]) which repeatedly occurs in the migration waters of cross-linked polyethylene (PE-X) pipes. In aqueous solution [1] is partially transformed to 3-(3,5-di‑tert‑butyl‑1‑hydroxy-4-oxo-2,5-cyclohexadien-1-yl)propionic acid ([2]). For a better understanding of the formation of [1] and its transformation into [2] an analytical method was established to allow the analysis of both species separately. Because of thermal instability [2] cannot be detected with GC–MS. Therefore, two methods were validated for a reliable and reproducible quantification: GC–MS for [1] and HPLC-MS/MS for both [1] and [2]. Comparative measurements of migration waters from PE-X pipes using GC–MS and HPLC-MS/MS methods showed that the concentrations of [1] detected with GC–MS corresponds to the sum of [1] and [2] measured with HPLC-MS/MS. In the migration waters [1] was detected in higher concentrations than [2]. The highest concentrations of [1], detected with GC–MS, were > 300 µg/L. The longer the materials are stored without contact with water, the more [1] is measured in the migration waters. Most of the previous values reported in the literature for [1] were based on semi-quantification. Hence, we compared results of the semi-quantitative determination according to EN 15768 with those of a quantitative method with a standard. The results gained with the semi-quantitative method represent less than 50% of the quantified values for the amount leaching from the pipes, which means that the semi-quantification method according to EN 15768 leads to a significant underestimation of [1]. Finally, stability assessment showed that [1] developed an equilibrium with [2] under acidic conditions, whereas it will completely be transferred to [2] at pH 10. At pH 7, it takes more than 50 days for [1] to reach an equilibrium with [2]. However, at increasing the temperature to 60 °C, [1] will be rapidly transformed into [2]. Besides [1] and [2], other currently unknown degradation products are formed. As there is no comprehensive toxicological assessment for both substances available today, our findings underline the need for regulatory consequences.