Glyphosate is the most commonly used herbicide in the United States. In the environment, glyphosate residues can either degrade into more toxic and persistent byproducts such as aminomethylphosphonic acid (AMPA) or environmentally benign species such as sarcosine or glycine. In this research, the birnessite-catalyzed degradation of glyphosate was studied under environmentally relevant temperatures (10-40 °C) using high-performance liquid chromatography, inductively coupled plasma mass spectrometry, nuclear magnetic resonance, and theoretical calculations. Our results show a temperature-dependent degradation pathway preference for AMPA and glycine production. The AMPA and glycine pathways are competitive at short reaction times, but the glycine pathway became increasingly preferred as reaction time and temperature increased. The measured free energy barriers are comparable for both the glycine and AMPA pathways (93.5 kJ mol-1 for glycine and 97.1 kJ mol-1 for AMPA); however, the entropic energy penalty for the AMPA pathway is significantly greater than the glycine pathway (-TΔS‡ = 26.2 and 42.8 kJ mol-1 for glycine and AMPA, respectively). These findings provide possible routes for biasing glyphosate degradation towards safer products, thus to decrease the overall environmental toxicity.
Keywords: Aminomethylphosphonic acid (AMPA); Birnessite; Degradation preference; Free energy; Glycine; Orthophosphate.
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