Determination of glyphosate, aminomethylphosphonic acid, and glufosinate in river water and sediments using microwave-assisted rapid derivatization and LC-MS/MS.

Glyphosate (N-phosphonomethyl glycine) and glufosinate (ammonium dl-homoalanin- 4-methyl phosphinate) are nonselective, broad-spectrum, and highly polar herbicides that are wildly used for weed control in aquatic systems and vegetation control in non-crop areas. Aminomethylphosphonic acid (AMPA) is the major degradation product of glyphosate. To address the concerns to its environmental residue and the possible adverse effects, the analytical methods by using microwave-assisted derivatization were developed for determining glyphosate, AMPA, and glufosinate in river water and sediments. The methods applied the 9-fluorenylmethyloxycarbonyl chloride (FMOC-Cl) derivatization for the analytes. The microwave heating is first-time applied to reduce the FMOC-reaction time of glyphosate, AMPA, and glyphosate in the environmental samples to less than 2.5 min. The microwave-assisted methods were successfully validated for river water and sediment. The linear ranges of 7.8-2000.0 ng/L and 0.78-100.0 ng/g were achieved by using 10 mL of water and 2 g of sediments. Glyphosate was found in 30/32% and 25/32% of 32 water and 32 sediments at 27.1-1353.9 ng/L and 2.4-189.6 ng/g levels. AMPA was found in 30/32% and 30/32% of 32 water and 32 sediments at 60.2-1509.0 ng/L and 1.8-233.6 ng/g levels. Glyphosate was found in 10/32% of 32 water at 14.8-503.1 ng/L levels. No glufosinate residue was observed for 32 sediments. The residues of glyphosate and AMPA were wildly detected in the river waters and sediments near the agricultural regions, and glufosinate was less detected. This is the first study that reported herbicide levels in water and sediment from Taiwan rural areas using microwave-assisted rapid derivatization, useful information for environmental management.