Determination of benzotriazoles in dishwasher tabs from Germany and estimation of the discharge into German waters

A method was developed for the determination of benzotriazoles (BTs) in dishwasher tabs. BTs consist of 1H-benzotriazole and/or tolyltriazole, i.e., a technical mixture of the two isomers 4-methylbenzotriazole and 5-methylbenzotriazole (5-MBT). The method consisted of weighing of an aliquot of the tab, addition of the internal standard 5-MBT, precipitation of the soaps with CaCl₂ and KOH, derivatization of the filtrate with acetic acid anhydride in a two-phase system, and analysis of the organic toluene layer by gas chromatography with mass spectrometry in the selected ion monitoring mode. Eleven of 12 different dishwasher tabs from the German market were tested positive with BTs ranging from 2 to 66 mg/tab. Dishwashing experiments were performed to show that at least 99 % of the BT amount used in the dishwasher did not remain on the dishes but was released into the wastewater treatment system. The annual release of BTs into the water system was estimated to be ~80 tons. Since 70 % or less of the BTs can be degraded in wastewater treatment plants, at least 24 tons are annually released into rivers in Germany.