Cross-resistance of barnyardgrass [Echinochloa crus-galli (L.) P. Beauv.] to aryloxyphenoxypropionate herbicides.

Managing emerged weeds that have evolved resistance to acetyl CoA carboxylase (ACCase)-inhibiting herbicides is a challenging task. A dose-response experiment was conducted on barnyardgrass biotypes resistant (R) and susceptible (S) to three aryloxyphenoxypropionate herbicides cyhalofop-butyl (CyB), fenoxaprop-ethyl (FeE), and quizalofop-ethyl (QuE) along with investigations into the potential resistance mechanism of these biotypes. The tested R barnyardgrass biotypes had strong resistance to CyB and FeE (resistant/susceptible ratio: 7.9-14.4) but weak resistance to QuE (resistant/susceptible ratio: 2.4-3.1). Absorption, translocation, and total metabolism of CyB and QuE were not associated with differences among S and R barnyardgrass biotypes. However, differences between S and R barnyardgrass were observed in production of active acid forms of each herbicide (cyhalofop-acid and quizalofop-acid). Production of cyhalofop-acid was >1.6-fold less in R barnyardgrass (3-8%) for 24 h after herbicide application than in the S barnyardgrass (8-16%). Meanwhile, production of quizalofop-acid was less in R barnyardgrass (< 14%) throughout the study period than in the S barnyardgrass (< 22%). Sequencing results of ACCase gene showed no difference between S and R barnyardgrass. Overall results show that a non-target-site resistance mechanism altering metabolism of CyB and QuE likely contributes to resistance of the barnyardgrass biotypes to these herbicides.

Absorption, translocation, and metabolism of florpyrauxifen-benzyl and cyhalofop-butyl in cyhalofop-butyl-resistant barnyardgrass [Echinochloa crus-galli (L.) P. Beauv.].

Dose-response experiments were conducted to assess the sensitivity of one susceptible and three putative resistant (R1, R2, and R3) barnyardgrass [Echinochloa crus-galli (L.) P. Beauv.] biotypes to florpyrauxifen-benzyl and cyhalofop-butyl alone and as a formulated premix. Subsequently, potential resistance mechanisms of the barnyardgrass were evaluated. Based on biomass reduction results, resistant/susceptible ratios were calculated for R1 (7.0-50), R2 (7.0-150), and R3 (18-214) biotypes. Absorption and translocation of [14C]-florpyrauxifen-benzyl decreased in R1 and R3 biotypes, but not for [14C]-cyhalofop-butyl. The metabolism of [14C]-florpyrauxifen-benzyl to [14C]-florpyrauxifen-acid was >2-fold less in resistant biotypes (9-11%) than in the susceptible biotype (23%). Moreover, the production of [14C]-florpyrauxifen-acid in susceptible barnyardgrass (not in the R biotypes) increased 3-fold when florpyrauxifen-benzyl and cyhalofop-butyl were applied in mixture compared to florpyrauxifen-benzyl applied alone. The tested barnyardgrass biotypes had no mutation in the Transport Inhibitor Response1, auxin-signaling F-box, and acetyl coenzyme A carboxylase genes. Although further studies on cyhalofop-butyl resistance with respect to analysis of specific metabolites are needed, our findings in this study demonstrates that the evolution of florpyrauxifen-benzyl resistance in multiple resistant barnyardgrass can be related to non-target-site resistance mechanisms reducing absorption and translocation of the herbicide and causing reduced conversion or rapid degradation of florpyrauxifen-acid.

Potential use of floating treatment wetlands established with Canna flaccida for removing organic contaminants from surface water.

Surface water bodies worldwide may be contaminated with various organic contaminants. In many cases, the actual toxicity thresholds to nontarget organisms are unknown, thus presenting unknown risks. This study evaluated the potential use of floating treatment wetlands (FTWs) planted with Canna flaccida (common name: Canna) for removing two pharmaceuticals (acetaminophen and carbamazepine) and one herbicide (atrazine) from contaminated water. Triplicate FTWs with varying plant densities were established in 378 L mesocosms. After dosing the mesocosms with the contaminants, water samples were collected over a 12-week period for analysis. The planted FTWs showed differing abilities for removing acetaminophen, atrazine, and carbamazepine. Plant densities on the FTWs did not affect dissipation of acetaminophen or atrazine, but did carbamazepine. All acetaminophen residues were removed from the water within 2 weeks, while all atrazine residues were removed within 12 weeks. Approximately, 79-92% of these residues removed were associated with the FTWs. In contrast, all of the carbamazepine was not removed after 12 weeks, at which time only 29-36.7% of the total removed was associated with the FTWs. Overall results suggest that FTWs established with C. flaccida are promising for removing trace concentrations of acetaminophen, atrazine, and carbamazepine from surface water.

Improved dissipation kinetic model to estimate permissible pre-harvest residue levels of pesticides in apples.

Prediction of residual concentrations of applied pesticides during the pre-harvest period may be required to ensure the safety of agricultural products. In this study, time-dependent dissipation trends of carbaryl (CB), kresoxim-methyl (KM), flubendiamide (FB), flufenoxuron (FN), bitertanol (BT), and chlorantraniliprole (CN) applied to apples at recommended and threefold greater doses were modeled to estimate pre-harvest residue limit concentrations (CPHRL) indicating permissible pesticide concentrations during the pre-harvest period. Double-exponential (DE) model results best fit the dissipation trends of all tested pesticides (correlation coefficients of 0.91-0.99) compared to zero-, first-, and second-order models. Among the pesticides examined, CB half-lives in apples of 2.9 and 6.6 days were the shortest, while those of FN (21.1-32.7 days) were the longest. The CPHRL values for each pesticide in apples were estimated with DE model parameter values and could be used to determine harvest dates for safe apples with pesticide concentrations below their maximum residue limits. Application of the DE model for CPHRL calculation provides more accurate information for farmers to produce agricultural products safe from pesticide residues.

Interpretation and estimation for dynamic mobility of chlorpyrifos in soils containing different organic matters.

The adsorption and removal behaviors of the organophosphate insecticide chlorpyrifos in two soils (AS and GW soils) with different organic matter contents were investigated to predict the dynamic residues in the soil environment. The adsorption test showed that the chlorpyrifos adsorptive power for the AS soil containing high organic matter content was greater than that for the GW soil. The extent of the time-dependent removal of chlorpyrifos in the tested soils was not significantly different except at 90 days after the treatment. The availability of a chemical-specific residue model developed in this study was statistically assessed to estimate the chlorpyrifos residue in soil solutions that could be absorbed into plants. The values modeled using the soil experimental data were satisfactory, having a mean deviation of 32% from the measured data. The correlation between the modeled and measured data was acceptable, with mean coefficients of correlation (R(2)) of 0.89. Furthermore, the average of the residual error was low at 0.43, which corresponded to a mean factor of -1.9. The developed model could be used as a critical tool to predict the subsequent plant uptake of chlorpyrifos.

Absorption, translocation, and metabolism of atrazine, carbamazepine, and sulfamethoxazole by the macrophyte Orange King Humbert canna lily (Canna × generalis L.H. Bailey (pro sp.) [glauca × indica]).

Canna × generalis L.H. Bailey (pro sp.) [glauca × indica] (common name: Orange King Humbert canna lily) has been reported as a promising plant species that can effectively remove contaminants of emerging concern (CECs), such as atrazine (ATZ), carbamazepine (CBZ), and sulfamethoxazole (SMX), from contaminated surface water. In the present study, absorption, translocation, and metabolism of such CECs in canna were examined using carbon-14-labeled ([14C]) analogues of each contaminant to understand the removal of each. Uptake/adsorption of the [14C]-CECs increased over time and was > 47.5% at the end of the 14-day study. The root-shoot translocation of [14C]-ATZ in canna was the greatest at 49.9-78.8%, followed by [14C]-CBZ (1.9-44.7%) and [14C]-SMX (3.3-6.0%). The cumulative transpiration of canna was correlated with absorption (R2 > 0.95) and root-shoot translocation (R2 > 0.97) magnitudes of [14C]-CECs in canna. Radiographic results revealed significant conversion of parent [14C]-CECs into other metabolites during the 14-day study. Metabolism of [14C]-ATZ and [14C]-CBZ occurred mainly in the shoots, whereas metabolism of [14C]-SMX occurred in the roots. Taken together, root-shoot redistribution and metabolism of CECs absorbed into canna can vary by transpiration volume as well as chemical properties.

Metabolic Exploration for Cyhalofop-Butyl Antagonism in Barnyardgrass [Echinochloa crus-galli (L.) P. Beauv.] Following Pretreatment of Malathion.

The present study investigated the effects of broad-spectrum metabolic inhibitors malathion (cytochrome P450 inhibitor) and/or 4-chloro-7-nitrobenzofurazan (NBD-Cl; glutathione S-transferase inhibitor) on the metabolism of cyhalofop-butyl (CyB) in barnyardgrass [Echinochloa crus-galli (L.) P. Beauv.] biotypes confirmed previously with multiple resistance to two herbicides CyB and florpyrauxifen-benzyl. The metabolic inhibitors were not effective at recovering the sensitivity of resistant barnyardgrass biotypes to CyB treated at the labeled rate (313 g ai ha-1). Rather, treatment with malathion followed by CyB caused antagonism, reducing the efficacy of CyB and promoting the growth of resistant biotypes. Pretreatment with malathion did not influence absorption/translocation of the applied form CyB and its conversion to the active herbicide form cyhalofop-acid (CyA), in both susceptible and resistant biotypes. In contrast, metabolism of the applied form (CyB) decreased 1.5 to 10.5 times by the malathion pretreatment. Taken together, the maintained CyA production against the reduced CyB metabolism could be the mechanism to account for the cause of CyB antagonism observed in barnyardgrass following malathion pretreatment. Additionally, the evolution of CyB resistance in barnyardgrass might be associated with reduced production of CyA in resistant biotypes, independent of activities of cytochrome P450 or GST enzymes.

Exploratory Analysis on Herbicide Metabolism and Very-Long-Chain Fatty Acid Production in Metolachlor-Resistant Palmer Amaranth (Amaranthus palmeri S. Wats.).

A Palmer amaranth (Amaranthus palmeri S. Wats.) biotype resistant to S-metolachlor was confirmed from crop fields in Arkansas, USA. This study investigated the metabolic effects of malathion (cytochrome P450 inhibitor) and 4-chloro-7-nitrobenzofurazan [NBD-Cl; glutathione S-transferase inhibitor] on the S-metolachlor-resistant A. palmeri biotype. Root elongation of the resistant biotype was 20% more inhibited by treatment of NBD-Cl (50 nM) and S-metolachlor (2 µM) in mixture than by treatment of S-metolachlor alone. Metabolites of S-metolachlor were 1.4-12.1 times greater produced in the resistant biotype for 7 d than in the susceptible standard. Production of cerotic acid, one of the very-long-chain fatty acids containing 26 carbons, was more reduced in the susceptible standard (3.8-fold) than in the resistant biotype (1.8-fold) by S-metolachlor treatment. Conclusively, evolution of S-metolachlor resistance observed in this study was likely associated with improved activity of glutathione S-transferases. Further studies are needed to genetically evaluate plant endogenous enzymes involving cerotic acid production.

Uptake of endosulfan isomers from soils by leafy vegetable lettuce: A comparative study between model-predicted and field-experimented results.

The organochlorine insecticide endosulfan has been classified as a persistent organic pollutant due to its long persistence and high toxicity, and banned in most countries. However, endosulfan residues are still detected in various environmental sites (even in non-agricultural areas) and have a likelihood to return to agricultural soils through various routes. In this study, time-dependent uptake of α- and ß-isomers of endosulfan by lettuce from soils was estimated using theoretical models which include parameters describing sorption/dissipation in soil and plants, plant transpiration, root-soil transfer, and plant growth. A chemical-specific residue (CSR) model developed in a previous study was used as a sub-model to estimate the portion of endosulfan residues in soils ready to be absorbed by lettuce, and the accuracy of the CSR model was verified by properly estimating concentrations of endosulfan isomers in soils with different organic matters; a low mean deviation (18.8 %) was observed between the modeled and measured values. Modeled results of ß-endosulfan using a soil-lettuce uptake model satisfactorily matched the experimentally measured results, with a moderate correlation (R2 > 0.79) and a low residual error (0.42) against a mean factor of -1.04. However, the uptake model showed the low potential to predict the soil-lettuce uptake of α-endosulfan (176.3 % mean deviation), probably due to not considering an intrinsic trait of ß-isomer converting to α-isomer. Although the improvement with more sophisticated parameters is needed, the plant uptake model developed in this study could be utilized to predict soil-lettuce uptake of at least ß-endosulfan and as a model template that may apply for other types of plants and contaminants.

Non-target-site resistance mechanism of barnyardgrass [Echinochloa crus-galli (L.) P. Beauv.] to florpyrauxifen-benzyl.

BACKGROUND: Florpyrauxifen-benzyl (FPB) is an arylpicolinate herbicide (Group IV) for barnyardgrass control in rice. One susceptible (Sus) and three putative FPB-resistant (R1, R2, and R3) barnyardgrass biotypes were selected based on resistant/susceptible (R/S) ratios obtained from dose-response tests and used to investigate the potential resistance mechanisms. RESULTS: Based on visual control results, the R/S ratios of barnyardgrass biotypes R1, R2, and R3 were 60-, 33-, and 16-fold greater than the Sus standard, respectively. Sequencing results of TIR1 and AFB genes in the tested barnyardgrass revealed no difference between Sus and R barnyardgrass biotypes. Absorption of [14 C]-FPB in Sus barnyardgrass increased over time and reached 90%, which was >10 percentage points greater than that in R biotypes. The [14 C]-FPB absorption in all R barnyardgrass equilibrated after 48 h. For both Sus and R barnyardgrass, most [14 C]-FPB absorbed was present in the treated leaf (79.8-88.8%), followed by untreated aboveground (9.5-18.6%) and belowground tissues (1.3-2.2%). No differences in translocation were observed. Differences between Sus and R barnyardgrass biotypes were found for FPB metabolism. Production of the active metabolite, florpyrauxifen-acid, was greater in Sus barnyardgrass (21.5-52.1%) than in R barnyardgrass (5.5-34.9%). CONCLUSION: In conclusion, reductions in FPB absorption and florpyrauxifen-acid production may contribute to the inability to control barnyardgrass with FPB. © 2021 Society of Chemical Industry.

Large-scale evaluation of physical drift and volatility of 2,4-D choline in cotton: a four-year field study.

BACKGROUND: Cotton with resistance to 2,4-d choline, glufosinate and glyphosate allows over-the-top use of these herbicides for postemergence weed control. Nontransgenic cotton is highly responsive to low rates of 2,4-d, causing concern among farmers when the herbicide is applied near the crop. Injury to nearby cotton following application of 2,4-d choline is sometimes blamed on volatilization of the herbicide. RESULTS: A large-scale experiment was conducted in 2018-2021 to better understand causes of damage to nearby sensitive cotton following an application of 2,4-d choline plus glufosinate-ammonium. The herbicides were applied to 0.4 ha in the center of a 4-ha non-Enlist cotton field. At 30 min after application, air samplers were established in the treated center and outside the treated area in cardinal directions. The 72-h cumulative air concentration of 2,4-d in the swath ranged from 3.3 to 7.1 ng m-3 , and most volatile residues (5.0-25.5 ng m-3 ) were detected in samplers established in the downwind direction directly adjacent to the treated field. Cotton plants in three downwind transects that were covered for 30 min after application were not damaged by 2,4-d, whereas noncovered plants along the downwind transects were injured. No cotton injury occurred outside the treated area, except in the downwind direction during application even though wind direction changed after application. CONCLUSION: 2,4-d choline volatilizes, but findings show that the volatilization is not sufficient to damage cotton in the neighboring area following applications, pointing to the importance of applicators understanding wind direction/shift during the application along with proximity of sensitive crops in the downwind direction. © 2022 Society of Chemical Industry.

Removal of organochlorine insecticide endosulfan in water and soil by Fenton reaction with ascorbic acid and various iron resources.

An assortment of Fenton (or Fenton-like) reaction treatment systems using various iron resources such as ferrous sulfate, ferric nitrate, commercial zerovalent iron (mZVI), or self-made ZVI (Fe-nanowire) were evaluated to effectively remove α- and ß-isomers of endosulfan (ED) from contaminated water and soil. Ascorbic acid (AA) was added as a chelation reagent to maintain the aqueous reaction of soluble iron. In the aqueous experiment, a combined treatment of 1% mZVI, 0.01 M AA, and 0.1 M H2O2 was determined to be the most effective method, showing 98-100% of ED removal within 24 h. The mZVI/AA/H2O2 treatment method was finally applied to ED-contaminated soil samples, and the application removed significant ED residues from both soil slurries (65-73%) and immobile soils containing small amount of moisture (64-66.2%). Overall results showed that the mZVI/AA/H2O2 treatment can be utilized as a potential technique to remediate both water and soil contaminated with ED.

Enhanced dissipation of trace level organic contaminants by floating treatment wetlands established with two macrophyte species: A mesocosm study.

This study evaluated removal efficiencies of six contaminants of emerging concern (CECs) in floating treatment wetland (FTW) mesocosms established with either Japanese Sweetflag (Acorus gramineus Sol. ex Aiton) or canna lilies (Canna Hybrida L. 'Orange King Humbert'). The CECs included: acetaminophen (APAP), atrazine (ATZ), carbamazepine (CBZ), perfluorooctanoic acid (PFOA), sulfamethoxazole (SMX), and 17ß-estradiol (E2). Each treatment was planted with different numbers of plants (i.e., 0, 10, 15, and 20), and the experiments lasted for 17 weeks. Dissipation of CECs was greater in planted treatments than in non-planted controls, and the planting number had little effect on dissipation of CECs. All residues of APAP and E2 dissipated rapidly within 2 weeks in all planted treatments. At the end of the experiment, residues of ATZ and SMX completely dissipated in the canna treatments, but not in the sweetflag treatments (75.8-87.6% and 96.3-97.1%, respectively). During the 17 week study, moderate dissipation of CBZ was observed in treatments including cannas (79.5-82.6%) and sweetflag (69.4-82.3%), while less dissipation was observed for PFOA (9.0-15.0% with sweetflag and 58.4-62.3% with cannas). Principal component analysis indicates that aqueous persistency of CECs and species of plants used influenced the dissipation of CECs in FTWs. Of the two species evaluated, canna was the most promising plant species for FTW systems designed to remove these CECs from surface water.

Accumulation characteristics of endosulfan soil residues in soybean and reduction in their phytoavailability by treatment with powdered activated carbon.

Powdered activated carbon (PAC) has been utilized for sorptive remediation of environmental sites contaminated with various organic chemicals. In the present study, time-dependent sorption/desorption characteristics of the α- and ß-isomers and a sulfate-metabolite of endosulfan (ED) were investigated in PAC-amended soils to determine the optimal PAC amendment dosage. Subsequently, ED phytoavailability to soybean (Glycine max Merr.) plants were examined in the presence or absence of PAC under restricted laboratory conditions. Based on the results of sorption/desorption tests, the optimal dosage of PAC amendment for ED-contaminated soils was determined as 1% (w/w), and at this dosage, all ED residues were sorbed completely onto the PAC-amended soils without any desorption. In soil amended with 1% PAC, the extents of ED accumulated by soybean plants were reduced by 89.4-100.0% within 20 days compared to those extents observed in unamended controls. Moreover, PAC treatment precluded the formation of the toxic metabolite ED-sulfate in either the soil or soybean plants. Therefore, PAC amendment in ED-contaminated soils could be highly effective for limiting uptake of ED into plants from contaminated soil and may be useful as an alternative method to produce safe food resources from contaminated arable soils.

Dissipation of fomesafen in fumigated, anaerobic soil disinfestation-treated, and organic-amended soil in Florida tomato production systems.

BACKGROUND: Fumigated, anaerobic soil disinfestation-treated (ASD), and organic-amended soil management strategies have been investigated as potential methyl bromide (MBr) alternatives for controlling diseases, nematodes, and weeds in soil. Nutsedge and broadleaf weed control using fomesafen has been reported to be comparable to MBr in normal cropping systems. There is no information on the fate of fomesafen used in combination with alternative practices. In this study, the fate of fomesafen in these alternative systems was measured by liquid chromatography-tandem mass spectrometry (LC/MS-MS) following extraction using a modified Quick Easy Cheap Effective Safe (QuEChERS) method. RESULTS: The reported half-life (DT50 ) values for fomesafen in the top 15 cm of soil were from 62.9 to 107.3 days. The DT50 values in organic-amended soil were higher than in ASD-treated soil in the top 15 cm. For all treatments, reductions in concentrations were positively correlated with lower redox potentials and organic matter content. Some leaching of fomesafen into the 16-30 cm zone was observed in all treatments. CONCLUSIONS: The DT50 values in this study were generally higher than those reported in previous studies performed at different locations. Due to increased losses of the herbicide and subsequent reduction in weed control, fomesafen is likely not to be suitable for effective weed control in systems using ASD techniques employing composted poultry litter and molasses. Integration of fomesafen using composted yard waste 1 (CYW1) and Soil Symphony Amendment (SSA) may result in acceptable weed control. Given that the soil was very sandy and the pH was higher than the pKa, fomesafen might leach deeper than 30 cm, particularly with the use of chemical soil fumigants (CSFs). © 2019 Society of Chemical Industry.

Bioconcentration factor-based management of soil pesticide residues: Endosulfan uptake by carrot and potato plants.

Uptake characteristics of endosulfan (ED), including α-, ß-isomers and sulfate-metabolites, from the soils by carrot and potato plants were investigated to establish a method that may be used to calculate recommended permissible soil contaminant concentrations (Cs, permissible) at time of planting so that maximum residue level (MRL) standards are not exceeded. The residues of ED were analyzed in soils treated with ED at concentrations of either 2 or 10 mg kg soil-1 and in the plants (carrots and potatoes) grown in such soils for 60-90 d. Presence of plants increased ED dissipation rates in soils in patterns that were best fit to a double-exponential decay model (R2 of 0.84-0.99). The ED uptake extent varied with type of crop, ED isomer, plant growth duration, and plant compartments. However, ED concentrations in all edible parts of crops eventually exceeded their maximum residue limits. Total ED bioconcentration factor (BCF), the ratio of soil ED concentration at planting time to that in edible part of each crop at harvest day, was found to decrease with time due to decreasing soil ED concentration and increasing plant biomass in a pattern that followed a first order kinetic model. Using this model, the Cs, permissible values, specific to the soils used in this study, were calculated to be 0.32 and 0.19 mg kg soil-1 for carrots and potatoes, respectively. The results and methods developed in this study may be utilized as a prediction tool to ensure crop safety from pesticide residues.

Comparison of theoretical and experimental values for plant uptake of pesticide from soil.

Pesticides that persist in soils may be taken up by the roots of plants. One way to assess plant uptake is to theoretically predict the extent of plant uptake using a mathematical model. In this study, a model was developed to predict plant uptake of pesticide residues in soils using various parameters, such as pesticide mobility within soil, plant transpiration stream, root-soil transfer rate, plant growth, and pesticide dissipation in either soils or plants. The accuracy of the model was evaluated by comparing the modeled concentrations with measured uptake concentrations of chlorpyrifos (CP) in lettuce, grown on treated soils with concentrations of approximately 10 and 20 mg kg-1 CP. Measured concentrations of CP in lettuce at 21, 30, and 40 d after planting were between the 5th and 95th percentiles of model variation. A high correlation coefficient of > 0.97 between modeled and measured concentrations was found. Coefficients of variation of mean factors to residual errors were between 25.3 and 48.2%. Overall, modeling results matched the experimental results well. Therefore, this plant uptake model could be used as an assessment tool to predict the extent of plant uptake of pesticide residues in soils.

Plant Uptake and Distribution of Endosulfan and Its Sulfate Metabolite Persisted in Soil.

The distributions of endosulfan (ED) residues (α-, ß-isomers, and sulfate-metabolite) in cucumbers grown in soils treated with ED at concentrations of 20 and 40 mg kg-1 were assessed using indoor and outdoor experiments. In all treatments, degradation rates of the α-isomer in soils were higher than that of the ß-isomer. In the indoor tests, uptake amounts of total ED by cucumbers, after 15 d of growth, were 7.8 and 14.5 mg kg-1 in 20 and 40 mg kg-1-treated pots, respectively. For growth time from 15 to 30 d, uptake amounts in 20 and 40 mg kg-1-treated pots were 3.8 and 7.9 mg kg-1, respectively. Outdoor tests resulted in smaller ED residues in cucumbers than those in indoor tests. In both indoor and outdoor tests, ED residues absorbed were highest in roots, and the α-isomer was the more frequently absorbed isomer. These results will be useful for determining management criteria for soil persistent pesticides.