In-situ formation of glyphosate and AMPA in activated sludge from phosphonates used as antiscalants and bleach stabilizers in households and industry

The herbicide glyphosate and aminomethyl phosphonic acid (AMPA), a transformation product of glyphosate and other aminopolyphosphonates are widespread pollutants in European rivers. We recently showed that besides rain-driven input after agricultural or urban herbicide application, municipal wastewater significantly contributes to glyphosate contamination in European rivers. The rather constant mass fluxes over the year, made an explanation by herbicide applications difficult. In our search for a new source of glyphosate and AMPA, we here provide experimental evidence that a certain aminopolyphosphonate, used as antiscalant and bleach stabilizer in household detergents and numerous industrial processes, is a precursor of both glyphosate and AMPA. During incubation experiments with diethylenetriamine penta(methylene phosphonic acid) (DTPMP) in fresh activated sludge, we observed the formation of glyphosate with yields ranging from 0.017 to 0.040 mol% and formation of AMPA in the range of 0.402 to 1.72 mol% after 72 h. Both compounds are formed from DTPMP and possible intermediates, but they are also further transformed themselves in consecutive reactions. Glyphosate formation from DTPMP was further proven by incubating ¹³C-labeled DTPMP, which transformed into ¹³C-glyphosate and ¹³C-AMPA. The addition of DTPMP to azide-treated activated sludge yielded similar or even higher glyphosate and AMPA concentrations indicating that abiotic processes dominate the transformation process. In order to judge the relevance of this in-situ formation of glyphosate and AMPA from the laundry additive DTPMP, we estimated the average concentrations in wastewater.