ABSTRACT
Glyphosate is a globally dominant herbicide. Here, we studied the degradation and microbial response to glyphosate application in a wetland soil in central Delaware for controlling invasive species (Phragmites australis). We applied a two-step solid-phase extraction method using molecularly imprinted polymers designed for the separation and enrichment of glyphosate and aminomethylphosphonic acid (AMPA) from soils before their analysis by ultra-high-performance liquid chromatography (UHPLC) and Q Exactive Orbitrap mass spectrometry methods. Our results showed that approximately 90 % of glyphosate degraded over 100 d after application, with AMPA being a minor (<10 %) product. Analysis of glyphosate-specific microbial genes to identify microbial response and function revealed that the expression of the phnJ gene, which codes C-P lyase enzyme, was consistently dominant over the gox gene, which codes glyphosate oxidoreductase enzyme, after glyphosate application. Both gene and concentration data independently suggested that C-P bond cleavage-which forms sarcosine or glycine-was the dominant degradation pathway. This is significant because AMPA, a more toxic product, is reported to be the preferred pathway of glyphosate degradation in other soil and natural environments. The degradation through a safer pathway is encouraging for minimizing the detrimental impacts of glyphosate on the environment.
Subject(s)
Glycine , Glyphosate , Herbicides , Soil Microbiology , Soil Pollutants , Wetlands , Glycine/analogs & derivatives , Glycine/metabolism , Herbicides/metabolism , Herbicides/chemistry , Soil Pollutants/metabolism , Delaware , Biodegradation, Environmental , Isoxazoles/metabolism , Lyases/metabolism , Lyases/genetics , Organophosphonates/metabolism , TetrazolesABSTRACT
Glyphosate, a widely used herbicide, is linked to a plethora of deleterious effects in both clinical and preclinical studies. Nevertheless, the effects of its main metabolite, aminomethylphosphonic acid (AMPA), whose half-life in soil is even longer than that of glyphosate, have been little explored. On this basis, as a first approach, in this work, we report that intraperitoneal (i.p.) administration of AMPA or glyphosate (at 10, 56, and 100 mg/kg) decreased, to a similar extent, plasma cholinesterase (ChE) activity in acutely exposed rats. Moreover, we designed an experimental protocol to analyze and compare the effects of AMPA and glyphosate on human plasma ChE activity; this protocol consisted of adding these compounds to human plasma to subsequently test the effects of this plasma on the contraction to acetylcholine (ACh) in the frog rectus abdominis muscle (an indirect estimate of ChE activity). Accordingly, this muscular contraction to ACh was evaluated before and after pre-incubation of ACh with (i) plasma alone, (ii) plasma with AMPA, and (iii) plasma with glyphosate. Our results indicate that AMPA, like glyphosate, decreased ChE activity in the plasma of rats (when given i.p.) and humans (when added in vitro), suggesting that both xenobiotics may exert similar toxicological effects.
ABSTRACT
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.