Analysis of glyphosate degradation in a soil microcosm

Highlights: • A comprehensive glyphosate biochemical reaction network was developed. • One functional group biodegraded up to 100% of injected glyphosate. • Various environmental conditions substantially decreased glyphosate biodegradation. • Glyphosate chemical degradation can overcome limited bacterial activity. Glyphosate (GLP) herbicide leaching into soil can undergo abiotic degradation and two enzymatic oxidative or hydrolytic reactions in both aerobic and anaerobic conditions; biotic oxidation produces aminomethylphosphonic acid (AMPA). Both GLP and AMPA are phytotoxic. A comprehensive GLP degradation reaction network was developed from the literature to account for the above pathways, and fifteen experimental data sets were used to determine the corresponding Michaelis-Menten-Monod (MMM) kinetic parameters. Various sensitivity analyses were designed to assess GLP and AMPA degradation potential against ${\text{O}}_2$ (aq) and carbon (C) availability, pH, and birnessite mineral content, and showed that bacteria oxidized or hydrolyzed up to 98% of GLP and only 9% of AMPA. Lack of a C source limited the GLP cometabolic hydrolytic pathways, which produces non-toxic byproducts and promotes AMPA biodegradation. Low bacterial activity in ${\text{O}}_2$ (aq)-limited conditions or non-neutral pH resulted in GLP accumulation. Birnessite mineral catalyzed fast GLP and AMPA chemodegradation reaching alone efficiencies of 79% and 88%, respectively, regardless of the other variables and produced non-toxic byproducts. Overall, ${\text{O}}_2$ (aq) and birnessite availability played the major roles in determining the partitioning of GLP and its byproducts mass fluxes across the reaction network, while birnessite, C availability, and pH affected GLP and AMPA biodegradation effectiveness.