We investigated the effects of four commercial formulations of herbicides (glyphosate [GLY], metsulfuron-methyl [MET], bispyribac-sodium [BIS], and picloram [PIC]) individually, and in three 50:50 mixtures (GLY–MET, GLY–BIS, GLY–PIC) on the common toad Rhinella arenarum (Anura: Bufonidae) tadpoles. Enzymatic parameters such as, glutathione S-transferase (GST), butyrylcholinesterase (BChE) and acetylcholinesterase (AChE) activities, as well as erythrocyte nuclear abnormalities (ENA) were studied. Interactions between herbicides in mixtures were evaluated and classified as additive, synergistic, or antagonistic. Toxicity results (48-h LC₅₀) showed that PIC was the most toxic herbicide, followed by BIS, GLY, and MET, while GLY–PIC was the most toxic mixture, followed by GLY–BIS, and GLY–MET. All commercial herbicide formulations and their mixtures significantly inhibited BChE activity in exposed tadpoles. The AChE activity was also inhibited by all herbicides and their mixtures, except by GLY–BIS. The inhibition of GST activity was only significant for GLY, MET, PIC, and GLY–MET. A significant increase in the frequency of ENA was found for tadpoles exposed either to commercial herbicide formulations or to mixtures, except for GLY. All the mixtures showed synergism for BChE activity while for AChE only the GLY–MET and GLY–PIC mixtures acted synergistically. GLY–MET showed synergism for GST, whereas for ENA, the mixture GLY–BIS was antagonistic. This study with R. arenarum tadpoles demonstrates that the interactions between three of the most intensively used herbicides in soybean crops results in synergistic effects on mortality and neurotoxicity and synergistic or additive effects in genotoxicity.

Metsulfuron-methyl is a sulfonylurea herbicide, primarily with postemergence activity but also with occasional pre-emergent activity, used for control of weeds and woody plants on agricultural lands and natural areas. The active ingredient is popular in Alaska as Ally XP formulation; little is known about its high-latitude environmental behavior and potential adverse impacts on soil health in cold regions. Our study determined field degradation rates at two experimental farms in Alaska and assessed whether laboratory-incubated soil amended at 1× or 100× label rates would adversely impact microbial community diversity. DT50 was observed at 4.12–5.13 days, with the compound below 1 μg/kg detection limit at 90 days. Interestingly, this is faster than the reported range of field half-lives in the literature (7–42 days). Microbial community composition was not affected by MSM at both 1× and 100× rates. High-latitude regions exhibit extreme summer photoperiods that may exacerbate the MSM degradation/dissipation rate; we postulate that timing of application may have large impacts on MSM attenuation.

Metsulfuron-methyl is a common active ingredient recommended for use in pre- and post-emergence control of annual grasses and broadleaf weeds in crops, usually applied with mineral oil as adjuvant to enhance its efficiency. Despite the increasing use of this herbicide, there are no information on its ecotoxicity effects to soil fauna. Avoidance and lethality tests were performed with earthworms and collembolans using tropical artificial soil contaminated with formulated products Ally® (600 g L⁻¹ metsulfuron-methyl) and Assist® (756 g L⁻¹ mineral oil) as adjuvant. Lethality test with earthworms showed no difference when tested with or without adjuvant. When Ally® was tested alone, it caused avoidance behavior only at high concentrations (5000 and 10,000 times field predicted dose). However, Assist® addition changed the response of soil invertebrates increasing the avoidance even at field predicted doses. The toxicity of the adjuvant was confirmed in tests exposing collembolans and earthworms to Assist® alone resulting in avoidance behavior. The results clearly show that the addition of mineral oil enhanced the ecotoxicity of metsulfuron-methyl. This study provides an important contribution to the knowledge on the toxicity of metsulfuron-methyl and indicates that adjuvants should be considered in risk assessment of pesticides, considering that under field conditions, these products are applied together.

The rapid biodegradation of metsulfuron-methyl in contaminated soil was studied in this paper. The wheat (Triticum aestivum L.) rhizosphere was well simulated by setting up a hydroponic system that allowed the aseptic wheat root exudates flow onto columns containing soil previously contaminated with metsulfuron-methyl. The root-colonizing strain Penicillium sp. containing highly effective degrading plasmid on metsulfuron-methyl was inoculated in the soil, with the bulk and sterile ones as control. In soil from columns that received root exudates from a planted (versus an unplanted) apparatus, there was a significant increase in the growth of the tolerant fungi and the degradation of metsulfuron-methyl. On the other hand, the inoculation of Penicillium sp. also notably enhanced the degradation of the target herbicide. The extent of stimulation was more than twice of that measured in bulk soil. The fastest rate of disappearance of the xenobiotic occurred in the amended inoculated microcosms with 8.6 days of the half-life. The main types of low molecular weight organic acids and amino acids in the root exudates was determined to be oxalic acid, succinic acid and threonine, alanine, proline, methionine, lysine, isoleucine and leucine. What's more, by means of applying metsulfuron-methyl once again, the acclimated soil microorganisms with Penicillium sp. inoculation could sustainable rapid degrade metsulfuron-methyl. The results show that inoculation of the root-colonizing Penicillium sp. in wheat rhizosphere may be an effective approach for the rapid detoxification of soil metsulfuron-methyl contamination.

The present paper discussed the comparison of the persistence and mobility of metsulfuron-methyl from a residue field trial experiment and simulation using a VARLEACH model. The residue field trial experiment was performed at Sungai Buloh Oil Palm Estate, Selangor. The plots were treated with metsulfuron-methyl at two treatment rates of 15 g a.i ha⁻¹ (T1) and 30 g a.i ha⁻¹ (T2). Soil samples were collected at 0, 1, 3, 7, 14, 21, 30, 60 and 90 days after treatment (DAT) and analysed subsequently by HPLC–UV. The results show that metsulfuron-methyl degraded rapidly in the soil with the half-life (t½) of 6.3 days in T1 and 7.9 days in T2. The simulation of VARLEACH model gave similar pattern of persistence and mobility of metsulfuron-methyl in the soil profile. However, total residues and the mobility of the metsulfuron-methyl were poorly simulated by the VARLEACH model due to consistent overestimation of the quantified residues. Results indicated that the metsulfuron-methyl lost more rapidly than the prediction values from VARLEACH model. In this case, simulation models which use transformation routines similar and which include additional degraded processes such as leaching, volatilisation, plant uptake or runoff could be considered. Albeit, overestimated values on the concentrations of metsulfuron-methyl are reported using VARLEACH model, the model still can be used as rapid and fast approach to predict the behaviour of pesticide at minimum cost.

Interactions between pesticides (paraquat, glyphosate, 2,4-D, atrazine, and metsulfuron methyl) and soil organic and inorganic components have been studied in batch experiments by performing adsorption, dissolution, and chemical and photochemical degradation under different conditions. The obtained results confirm that the affinity of a pesticide to the solid surface depends on the nature of both and shows that each reactant strongly affects the mobility of the other one, e.g., anionic pesticides promote the dissolution of the solid humic acid but if this last is retained into the inorganic matrix enhances the adsorption of a cationic pesticide. Adsorption also seems to protect the bonded specie to be chemical degraded, such as shown in two pesticide/clay systems at constant pH. The use of mesoporous silicas could result in a good alternative for pesticide remediation. In fact, the solid shows high adsorption capacity towards paraquat and its modification with TiO₂ nanoparticles increases not only the pesticide adsorption but also seems to catalyze its degradation under UV light to less-toxic metabolites. UV-VIS spectroscopy was relevant and novel in such sense. Electrostatic interactions, hydrogen and coordinative bonds formations, surface complexations and hydrophobic associations play a key role in the fate of mentioned pesticides on soil and ground/surface water environments.

Sorption-desorption behavior of six pesticides and some degradation products was assessed on seven agricultural volcanic and nonvolcanic soils belonging to Andisol, Ultisol, Mollisol, and Alfisol orders. The global interpretation of sorption data was performed by principal component analysis. Results showed exceptionally high sorption of glyphosate and aminomethylphosphonic acid (AMPA) (the breakdown product) on volcanic soils (K f > 1500 μg¹ ⁻ ¹ / ⁿ mL¹ / ⁿ g⁻¹) related mainly to contents of amorphous aluminum oxides (Andisols) and crystalline minerals (Ultisols). The lower sorption on nonvolcanic soils was associated to low organic matter contents and lack of significant minerals. Metsulfuron-methyl and 3,5,6-trichloro-2-pyridinol (metabolite of chlorpyrifos) were weakly to substantially sorbed on Andisols and Ultisols, but the first one was not sorbed at pH > 6.4, including nonvolcanic soils. The metabolite of diazinon, 2-isopropyl-4-methyl-6-hydroxypyrimidine, was weakly sorbed on all soils (K f = 0.4 to 3.6 μg¹ ⁻ ¹ / ⁿ mL¹ / ⁿ g⁻¹). Acidic compounds would be lixiviated in Mollisols and Alfisols, but they could leach also in Andisols and Ultisols if they reach greater depths. Atrazine and deethylatrazine sorption was related to organic carbon content; therefore, they were weakly retained on nonvolcanic soils (K f = 0.7 to 2.2 μg¹ ⁻ ¹ / ⁿ mL¹ / ⁿ g⁻¹). Chlorpyrifos was highly sorbed on all soils reaching K OC values of >8000. Finally, the significant retention of chlorothalonil and diazinon on Mollisols and Alfisols in spite of their low OC contents showed the contribution of clay minerals in the sorption process.

Soil contamination caused by long-term application of metsulfuron-methyl and tribenuron-methyl has become an issue of increasing concern. In our previous study, strain Chenggangzhangella methanolivorans CHL1, capable of efficiently degrading sulfonylurea herbicides, was isolated. Here, the bioremediation potential of strain CHL1 was assessed for soil polluted with metsulfuron-methyl or tribenuron-methyl in a pot experiment. The growth parameters of waxy maize were measured on day 21 of the pot experiment. Additionally, the residues of metsulfuron-methyl and tribenuron-methyl in soils were analyzed, and the soil microbial community was investigated using a phospholipid fatty acids (PLFAs) method on days 1, 7, 14, and 21. The results indicated that strain CHL1 greatly accelerated the degradation of metsulfuron-methyl and tribenuron-methyl in soils. The degradation rates in the treatments inoculated with strain CHL1were all more than 91% after 7 days, significantly higher than the 25–36% degradation measured in non-inoculated treatments. Furthermore, strain CHL1 reduced the negative effects of tribenuron-methyl and metsulfuron-methyl on waxy maize growth, especially the primary root length. Moreover, inoculation with strain CHL1 also reduced the effects of tribenuron-methyl and metsulfuron-methyl on soil microbial biomass, diversity, and community structure. The present study demonstrates that strain CHL1 has great potential application to remediate soil contaminated with metsulfuron-methyl or tribenuron-methyl.