Radiometric approaches with carbon-14-labeled molecules for determining herbicide fate in plant systems.

Weeds cause economic losses in cropping systems, leading to the use of 1.7 million tons of herbicides worldwide for weed control annually. Once in the environment, herbicides can reach non-target organisms, causing negative impacts on the ecosystem. Herbicide retention, transport, and degradation processes determine their environmental fate and are essential to assure the safety of these molecules. Radiometric strategies using carbon-14 herbicides (14C) are suitable approaches for determining herbicide absorption, translocation, degradation, retention, and transport in soil, plants, and water. In this work, we demonstrate how 14C-herbicides can be used from different perspectives. Our work focused on herbicide-plant-environment interactions when the herbicide is applied (a) through the leaf, (b) in the soil, and (c) in the water. We also quantified the mass balance in each experiment. 14C-mesotrione foliar absorption increased with oil and adjuvant addition (5-6 % to 25-46 %), and translocation increased only with adjuvant. More than 80 % of 14C-quinclorac and 14C-indaziflam remained in the soil and cover crops species absorbed less than 20 % of the total herbicides applied. In water systems, Salvinia spp. plants removed 10-18 % of atrazine from the water. Atrazine metabolism was not influenced by the presence of the plants. The radiometric strategies used were able to quantify the fate of the herbicide in different plant systems and the mass balance varied from 70 % to 130 %. Importantly, we highlight a critical and practical view of tracking herbicides in different matrices. This technique can aid scientists to explore other pesticides as environmental contaminants.

Biochar obtained from eucalyptus, rice hull, and native bamboo as an alternative to decrease mobility of hexazinone, metribuzin, and quinclorac in a tropical soil.

Mobile herbicides have a high potential for groundwater contamination. An alternative to decrease the mobility of herbicides is to apply materials with high sorbent capacity to the soil, such as biochars. The objective of this research was to evaluate the effect of eucalyptus, rice hull, and native bamboo biochar amendments on sorption and desorption of hexazinone, metribuzin, and quinclorac in a tropical soil. The sorption-desorption was evaluated using the batch equilibrium method at five concentrations of hexazinone, metribuzin, and quinclorac. Soil was amended with eucalyptus, rice hull, and native bamboo biochar at a rate of 0 (control-unamended) and 1% (w w-1), corresponding to 0 and 12 t ha-1, respectively. The amount of sorbed herbicides in the unamended soil followed the decreasing order: quinclorac (65.9%) > metribuzin (21.4%) > hexazinone (16.0%). Native bamboo biochar provided the highest sorption compared to rice hull and eucalyptus biochar-amended soils for the three herbicides. The amount of desorbed herbicides in the unamended soil followed the decreasing order: metribuzin (18.35%) > hexazinone (15.9%) > quinclorac (15.1%). Addition of native bamboo biochar provided the lowest desorption among the biochar amendments for the three herbicides. In conclusion, the biochars differently affect the sorption and desorption of hexazinone, metribuzin, and quinclorac mobile herbicides in a tropical soil. The addition of eucalyptus, rice hull, and native bamboo biochars is a good alternative to increase the sorption of hexazinone, metribuzin, and quinclorac, thus, reducing mobility and availability of these herbicides to nontarget organisms in soil.

The role of land use, management, and microbial diversity depletion on glyphosate biodegradation in tropical soils.

Land use and management changes affect the composition and diversity of soil bacteria and fungi, which in turn may alter soil health and the provision of key ecological functions, such as pesticide degradation and soil detoxification. However, the extent to which these changes affect such services is still poorly understood in tropical agroecosystems. Our main goal was to evaluate how land-use (tilled versus no-tilled soil), soil management (N-fertilization), and microbial diversity depletion [tenfold (D1 = 10-1) and thousandfold (D3 = 10-3) dilutions] impacted soil enzyme activities (ß-glycosidase and acid phosphatase) involved in nutrient cycles and glyphosate mineralization. Soils were collected from a long-term experimental area (35 years) and compared to its native forest soil (NF). Glyphosate was selected due to its intensive use in agriculture worldwide and in the study area, as well as its recalcitrance in the environment by forming inner sphere complexes. Bacterial communities played a more important role than the fungi in glyphosate degradation. For this function, the role of microbial diversity was more critical than land use and soil management. Our study also revealed that conservation tillage systems, such as no-tillage, regardless of nitrogen fertilizer use, mitigates the negative effects of microbial diversity depletion, being more efficient and resilient regarding glyphosate degradation than conventional tillage systems. No-tilled soils also presented much higher ß-glycosidase and acid phosphatase activities as well as higher bacterial diversity indexes than those under conventional tillage. Consequently, conservation tillage is a key component for sustaining soil health and its functionality, providing critical ecosystem functions, such as soil detoxification in tropical agroecosystems.

Sorption-desorption and biodegradation of sulfometuron-methyl and its effects on the bacterial communities in Amazonian soils amended with aged biochar.

Sulfometuron-methyl is a broad-spectrum herbicide, used throughout Brazil; however, its environmental impacts in biochar (BC) amended soils is not fully understood. Biochar is known to enhance soil quality but can also have undesired effects such as altering the bioavailability and behavior of herbicides. Microbial communities can degrade herbicides such as sulfometuron-methyl in soils; however, they are known to be affected by BC. Therefore, it is important to understand the tripartite interaction between these factors. This research aimed to evaluate the sorption-desorption and biodegradation of sulfometuron-methyl in Amazonian soils amended with BC, and to assess the effects of the interactions between BC and sulfometuron-methyl on soil bacterial communities. Soil samples were collected from field plots amended with BC at three doses (0, 40 and 80 t ha-1) applied ten years ago. The herbicide sorption and desorption were evaluated using a batch equilibrium method. Mineralization and biodegradation studies were conducted in microcosms incubated with 14C-sulfometuron-methyl for 80 days. Systematic soil sampling, followed by DNA extraction, quantification (qPCR) and 16S rRNA amplicon sequencing were performed. The presence of BC increased the sorption of the herbicide to the soil by 11% (BC40) and 16% (BC80) compared to unamended soil. The presence of BC also affected the degradation of 14C-sulfometuron-methyl, reducing the mineralization rate and increasing the degradation half-life times (DT50) from 36.67 days in unamended soil to 52.11 and 55.45 days in BC40 and BC80 soils, respectively. The herbicide application altered the bacterial communities, affecting abundance and richness, and changing the taxonomic diversity (i.e., some taxa were promoted and other inhibited). A tripartite interaction was found between BC, the herbicide and soil bacterial communities, suggesting that it is important to consider the environmental impact of soil applied herbicides in biochar amended soils.

Phytoremediation of quinclorac and tebuthiuron-polluted soil by green manure plants.

Quinclorac and tebuthiuron are residual herbicides that may remain in the soil longer than for the cropping season. The objective of this research was to evaluate the use of green manure plants to remediate soils treated with quinclorac and tebuthiuron. Soils were separately treated with 14C-quinclorac and 14C-tebuthiuron at 266.4 and 132 g ha-1, respectively. After 21 days, four green manure plants, namely Crotalaria spectabilis, Canavalia ensiformis, Stizolobium aterrimum, and Lupinus albus, were separately sown in the treated soils. Overall, all four species absorbed more 14C-tebuthiuron [C. ensiformes (22.49%), S. aterrimum (16.71%), L. albus (15%), and C. spectabilis (4.48%)] than 14C-quinclorac [C. ensiformis (13.44%), L. albus (10.02%), S. aterrimum (6.2%), and C. spectabilis (1.75%)]. Quinclorac translocation in all four plants was greater in young leaves compared to old leaves, cotyledons, or roots, and 14C-tebuthiuron translocation in all four plant species was greater in old leaves and cotyledons compared to young leaves or roots. Regardless of the differences in translocation between the two herbicides, the four green manure plants are capable to remediate soils that have been treated with quinclorac and tebuthiuron. However, C. ensiformis is more efficient for the remediation of tebuthiuron-treated soil compared to the other plants.

Fertiactyl® in mixture with glyphosate decreases herbicide absorption and translocation in coffee seedlings.

The application of glyphosate to coffee crops can cause injuries to plants. Fertiactyl® foliar fertilizer reduces injuries when mixed with glyphosate; however, it is important to establish which mechanisms are responsible for this protective action. This study aimed to evaluate the absorption and translocation of glyphosate applied separately and in mixture with Fertiactyl® in coffee seedlings. Absorption and translocation were performed with 14C-glyphosate applied separately and in mixture with Fertiactyl® at 0, 6, 12, 24, 48, 96, and 144 hours after application (HAA). Most of the 14C-glyphosate applied to coffee seedlings was not absorbed. The 14C-glyphosate applied separately had a higher absorption by coffee seedlings (6.5%) than in a mixture with Fertiactyl® (2.7%) at 144 HAA. The maximum translocation of the 14C-glyphosate applied separately was 0.69% at 81.2 HAA and in mixture with Fertiactyl® was 0.41% at 41.2 HAA. The treated leaves retained a higher percentage of 14C-glyphosate when applied separately (5.6% at 144 HAA) than in a mixture with Fertiactyl® (2.2% at 144 HAA). Low translocation (<1%) for the rest of the plant shoots was observed both for the 14C-glyphosate applied separately and in combination with Fertiactyl®. Therefore, Fertiactyl® decreased the absorption and translocation of 14C-glyphosate in coffee seedlings.

Indaziflam sorption-desorption and its three metabolites from biochars- and their raw feedstock-amended agricultural soils using radiometric technique.

This study aimed to characterize the effect of amending soils with biochars derived from soybean residues, sugarcane bagasse, and wood chips on the sorption-desorption of indaziflam and indaziflam-triazinediamine (FDAT), indaziflam-triazine-indanone (ITI), and indaziflam-carboxylic acid (ICA) metabolites applied to soils from three Midwestern U.S. states, a silt loam and a silty clay loam. Biochars produced from different feedstock were used as soil amendments and compared with raw feedstock. Sorption-desorption experiments of indaziflam and its three metabolites were performed using the batch equilibration method and analyzed for 14C activity by liquid scintillation counting (radiometric technique). In all soils, the use of organic amendments promoted greater sorption and less desorption of indaziflam and ITI. The addition of biochar to soils promoted greater sorption of the four tested chemical products compared with the corresponding raw materials. Among the biochars, grape wood chips showed greater potential in sorb indaziflam and ITI. In general, none of the biochars affected the sorption and desorption of FDAT and ICA. Characterization of biochar to be used as a soil amendment (immobilizer) is highly recommended prior to field addition to optimize the sorption process and to prevent increased soil and water contamination of indaziflam and its metabolites following biochar addition.

Potential of Egeria densa and Pistia stratiotes for the phytoremediation of water contaminated with saflufenacil.

Saflufenacil is an herbicide that is leachable in soil and has the potential to contaminate groundwater, besides having moderate toxicity to aquatic organisms. Some macrophyte species may interfere with the availability of herbicides in water, increasing dissipation in this environment. Thus, the objective of this work was to evaluate the absorption and dissipation of 14C-saflufenacil in water by Egeria densa and Pistia stratiotes. Dissipation was performed with 14C-saflufenacil applied directly in water and quantified by liquid scintillation spectrometry (LSS). The evaluation times were 0, 3, 6, 24, 48, 72 and 96 h after application (HAA) for E. densa and 0, 12, 24, 36, 48, 60, 84 and 108 HAA for P. stratiotes. Absorption was analyzed through plant combustion in a biological oxidizer. The presence of the macrophytes increased the dissipation of 14C-saflufenacil in water. The half-life time (DT50) of the herbicide decreased by 82.6% in the presence of E. densa at 96 HAA. For P. stratiotes, the reduction in DT50 was 94.8% at 108 HAA. The absorption of 14C-saflufenacil was low for both macrophytes during the evaluated time. However, the macrophytes E. densa and P. stratiotes showed potential for the phytoremediation of water contaminated with saflufenacil.

Effect of Fertiactyl® on the absorption and translocation of 14C-glyphosate in young eucalyptus plants.

Fertiactyl® is a foliar fertilizer with the potential to minimize the phytotoxicity effects caused by glyphosate drift in eucalyptus plants. As the interactions of the glyphosate and Fertiactyl® in tank mix on the plant behavior are not yet known, the objective was to evaluate the absorption and translocation of 14C-glyphosate, applied isolated and mixed in tank with Fertiactyl®, in young eucalyptus plants (clone I-144, Eucalyptus urophylla x E. grandis). The addition of Fertiactyl® to the mixture of 14C-glyphosate reduced the absorption by 94.3% in relation to the total absorbed at the end of the evaluation compared to plants treated only with 14C-glyphosate, i.e., Fertiactyl® protected the eucalyptus plants of the glyphosate intoxication by drift. The translocation rates from the treated leaves to the rest of the shoots and roots were low (<2% of the total recovered) in both treatments, suggest that restricted translocation is a mechanism of natural tolerance to glyphosate in plants of clone I-144. It is concluded that Fertiactyl®, mixed in the solution with glyphosate, protects young eucalyptus plants against glyphosate drift by reducing the amount of herbicide absorbed.

Using 14C-glyphosate to investigate the distribution of two formulations in transgenic glyphosate-resistant soybean.

Glyphosate residues in grain can be explained by the concentrations and formulations of glyphosate products. This study aimed to evaluate the residues from glyphosate formulations labeled with 14C-glyphosate applied to leaves of glyphosate-resistant soybean (GRS) in two life cycles by liquid scintillation spectrometry. Different plant tissues were analyzed after the end of the plants' life cycles. The experimental design was four repetitions of three treatments: Roundup® Original, Roundup Ready®, and unformulated glyphosate (control). The application of the dosing solution was 120 µL on the first four trifoliate leaves (10 µL per leaflet) of each plant, deposited manually with a 1-µL dispenser. All treatment solutions were calculated at a 1.2 kg a.e ha-1 of glyphosate. Glyphosate formulations of Roundup® Original and Roundup Ready® increased 14C-glyphosate distribution in GRS compared to the unformulated herbicide, regardless of the experiment (first or second cycle). Overall, the percentages of total radioactivity applied (18.33 kBq) found in grains were less than 5%. Grains, stems, and leaves showed the highest levels of herbicide residues compared to other parts of the plant. Despite the Roundup Ready® formulation having increased residues, the highest value found in grains, 1.95 mg kg-1, was less than 10 mg kg-1, the maximum residue limit (MRL) in Brazil.