The adsorption from chloroform solution of the herbicide diclofop, (RS)-2-(4-(2,4-dichlorophenoxy)phenoxy)propionic acid, and its methyl ester diclofop-methyl on Cu2+-, Al3+-, and Fe3+-exchanged bentonite samples was investigated. For comparison, the complexes formed by diclofop were synthesized and studied. Diclofop adsorbed on the clays and formed carboxylate bonds to the interlayer ions. Diclofop-methyl also adsorbed, but its interaction involved the formation of hydrogen bonds with water molecules in the interlayer. Traces of diclofop were observed in both the solution and the clays after adsorption of diclofop-methyl, indicating that some hydrolysis of the ester to the corresponding acid occurred. Thus, pesticides forming neutral complexes with interlayer cations in montmorillonite in soils may be extractable by solvents and therefore released into the environment.

The sustainable management of herbicides is critical to modern agriculture and the environment. This article examines the evolution and environmental implications of herbicide use in Saskatchewan, Canada, agriculture. It quantifies changes in herbicide use and their environmental impacts by analyzing farm-level herbicide use data from 1991 to 1994 and from 2016 to 2019 through the environmental impact quotient. Results confirm significant reductions in both environmental and toxicological impacts of herbicides used, underlining the pivotal shift from tillage-based weed control to herbicide-resistant cropping systems. The environmental impact of the top five herbicides (glufosinate, glyphosate, clethodim, imazamox, and 2,4-D) used from 2016 to 2019 is 65% lower than that for those herbicides (MCPA, 2,4-D, bromoxynil, diclofop-methyl, and trifluralin) used from 1991 to 1994, with a 45% reduction in the active ingredient applied per acre. Despite increased herbicide use due to more crop acres being seeded, the findings highlight a marked improvement in the sustainability of herbicide use, affirming the importance of technological advancements in agriculture. This research contributes valuable insights into long-term trends in herbicide use, offering a practical framework for informed decisions aligning with sustainable agricultural practices as well as reduced biodiversity impacts.

Field surveys were conducted across the Blacklands region of Texas during 2016 and 2017 to document the distribution of herbicide-resistant Lolium spp. infesting winter wheat production fields in the region. A total of 68 populations (64 Italian ryegrass, four perennial ryegrass) were evaluated in a greenhouse for sensitivity to herbicides of three different modes of action: an acetolactate synthase (ALS) inhibitor (mesosulfuron-methyl), two acetyl-coenzyme-A carboxylase (ACCase) inhibitors (diclofop-methyl and pinoxaden), and a 5-enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitor (glyphosate). Herbicides were applied at twice the label-recommended rates for mesosulfuron-methyl (29 g ai ha−1), diclofop-methyl (750 g ai ha−1), and pinoxaden (118 g ai ha−1); and at the recommended rate for glyphosate (868 g ae ha−1). The herbicide screenings were followed by dose-response assays of the most-resistant ryegrass population for each herbicide at eight rates (0.5, 1, 2, 4, 8, 16, 32, and 64×), compared with a susceptible population at six rates (0.0625, 0.125, 0.25, 0.5, 1, and 2×). The initial screening and dose-response experiments were conducted in a completely randomized design with three replications and two experimental runs. Survivors (<80% injury) were characterized as highly resistant (0% to 20% injury) or moderately resistant (21% to 79%). Results showed that 97%, 92%, 39%, and 3% of the Italian ryegrass populations had survivors to diclofop-methyl, mesosulfuron-methyl, pinoxaden, and glyphosate treatments, respectively. Of the four perennial ryegrass populations, three were resistant to diclofop-methyl and mesosulfuron-methyl, and one was resistant to pinoxaden as well. Perennial ryegrass populations did not exhibit any resistance to glyphosate. Dose-response assays revealed 37-, 196-, and 23-fold resistance in Italian ryegrass to mesosulfuron-methyl, diclofop-methyl, and pinoxaden, respectively, compared with a susceptible standard. One Italian ryegrass population exhibited three-way multiple resistance to ACCase-, ALS-, and EPSPS-inhibitors. The proliferation of multiple herbicide–resistant ryegrass is a challenge to sustainable wheat production in Texas Blacklands and warrants diversified management strategies.

Following 15 yr of successful use, glyphosate failed to control a population of the widespread grass weed rigid ryegrass in Australia. This population proved to be resistant to glyphosate in pot dose-response experiments conducted outdoors, exhibiting 7- to 11-fold resistance when compared to a susceptible population. Some cross-resistance to diclofop-methyl (about 2.5-fold) was also observed. Similar levels of control of the resistant and susceptible populations were obtained following application of amitrole, chlorsulfuron, fluazifop-P-butyl, paraquat, sethoxydim, sirnazine, or tralkoxydim. The presence of glyphosate resistance in a major weed species indicates a need for changes in glyphosate use patterns.

The influence of wheat variety on the dose-response of annual ryegrass to diclofop-methyl (POST) was examined in the field in 1992 and 1993 in southern New South Wales, Australia. The aim was to determine if planting a strongly competitive variety of wheat improved control of annual ryegrass at reduced doses of diclofop-methyl. Suppression of ryegrass was dependent on herbicide dose, season, and wheat variety. In the absence of herbicide, dry matter (DM) production of annual ryegrass at 300 plants m−2 at anthesis was 500 g ha−1 with Dollarbird and Katunga compared to 1000 g ha−1with Rosella or Shrike in 1992. In 1993, DM was approximately 150 g ha−1 with Dollarbird or Katunga, and 350 g ha−1with Shrike or Rosella. Ryegrass DM was reduced by diclofop-methyl to a greater extent, relative to the weedy unsprayed controls, with less competitive varieties Rosella and Shrike than with the more competitive Dollarbird or Katunga. Diclofop-methyl at 0.28 kg a.i. ha−1 reduced DM of ryegrass growing with Katunga to less than 100 g m−2 in 1992, compared to more than 200 g m2 with the other varieties. In 1993, diclofop-methyl was more effective on ryegrass, and the same dose reduced ryegrass DM to almost zero in all varieties. Grain yields in unsprayed weedy controls of Dollarbird and Katunga were reduced approximately 20% by annual ryegrass compared with yields achieved with herbicides in both years. Yields of Rosella and Shrike in the unsprayed controls were reduced about 40% in 1992 and 60% in 1993. Only small increases in grain yields of all varieties occurred from diclofop-methyl doses above 0.13 kg a.i. ha−1. Poorly competitive varieties were dependent on herbicides to achieve grain yield potential and had a greater risk of weed survival when herbicide efficacy was reduced. In contrast, strongly competitive varieties, likely to retard build-up of weed seed in the soil, are less dependent on herbicides to achieve grain yield potential, and therefore result in reduced weed control cost.

At least 57 weed species, including both dicots and monocots, have been reported to have biotypes selected for resistance to the triazine herbicides. In addition, at least 47 species have been reported to have biotypes resistant to one or more of 14 other herbicides or herbicide families. These herbicides include the aryloxyphenoxypropionics, bipyridiliums, dinitroanilines, phenoxys, substituted areas, and sulfonylureas, with two or more resistant biotypes each, as well as several other herbicides in which resistance is less well documented. Although evolved resistance presents a serious problem for chemical weed control, it has also offered new potential for transferring herbicide resistance to crop species. Mechanisms of resistance that are due to single or a few genes have become the focus of biotechnology, as the probability of their successful transfer to crop species is high.

Glyphosate is the world's most widely used herbicide. It is nonselective and has been used to control a broad range of weed species for the past 20 yr, without the appearance of resistant weed biotypes. However, a biotype of Lolium rigidum from a field in Northern Victoria, Australia, in which glyphosate had been used for the past 15 yr, failed to be controlled by label recommended rates. Based on LD50 values from pot dose-response experiments, this biotype exhibited resistance to glyphosate and was nearly 10-fold more resistant compared to the susceptible biotypes tested. The biotype was resistant to three different salts of glyphosate. The biotype was also nearly threefold more resistant to diclofop-methyl but was susceptible to other commonly used selective and broad-spectrum herbicides. Between the two-leaf and tillering stages of development, a susceptible biotype exhibited a small but significant decrease in tolerance to glyphosate, whereas tolerance of the resistant biotype remained unchanged with age. The resistant phenotype was verified in experiments in which seed was germinated in the presence of glyphosate. Observations on shoot and root growth of seedlings in these experiments suggested that the resistance mechanism might be associated more with the shoot than with the root.

An assessment was made of various parameters to measure growth of soybean [Glycine max (L.) Merr. ‘Wilkin’] and einkorn (Triticum monococcum L.) cell suspension cultures to establish convenient methods of screening the effects of chemicals. Methods assessed were settled cell volumes, packed cell volumes, absorbance at 525 nm of sonicated aliquots, dry weights (of aliquots or entire flask contents), and electrical conductivity and pH of the culture medium. Settled cell volumes, conductivity, and dry-weight changes were the most useful of the methods tested for determining the phytotoxicity of a nonionic linear alcohol ethylene oxide detergent (an adduct of 1-dodecanol containing eight ethylene oxide units) and the methyl ester of diclofop {2-[4-(2,4-dichlorophenoxy)phenoxy] propanoic acid}. Because 3 to 4 weeks were required to assess whether the cultures could grow out of the initial inhibition by the detergent or herbicide, none of the methods was rapid. Advantages and disadvantages of the various methods and their relative values for screening compounds are described.

The response of littleseed canarygrass biotypes to isoproturon, pendimethalin, and diclofop-methyl was evaluated in India, in pot studies and the field during the winters of 1991 to 1992 and 1992 to 1993. Some biotypes of littleseed canarygrass were resistant to isoproturon but cross-resistance to pendimethalin and diclofop-methyl was not confirmed. The resistant biotype required a higher dose of diclofop-methyl than the susceptible biotype. Variations in the response of littleseed canarygrass biotypes were not due to isoproturon formulation. Resistant biotypes required 2 to 8 times more isoproturon than a susceptible biotype for the same level of control. Diclofop-methyl at 1.0 kg ai/ha applied at the 2- to 3-leaf stage of littleseed canarygrass in pot experiments and PRE pendimethalin at 1.5 kg ai/ha in field trials controlled resistant biotypes. Field surveys of the affected areas revealed that resistance in littleseed canarygrass is more prevalent in rice-wheat rotations compared to other crop sequences. Control of littleseed canarygrass with isoproturon dropped from 78 to 21% from 1990 to 1993.

A Lolium multiflorum Lam. biotype resistant to diclofop-methyl was found in a Triticum aestivum field in France (Normandy) that had been treated for several years with diclofop-methyl. Based on plant survival evaluated 21 d after herbicide application, the biotype exhibited a high level of resistance to diclofop-methyl and moderate resistance to CGA-184927-propargil and PP-604. The resistant biotype exhibited a small increase in tolerance to haloxyfop-methyl, quizalofop-ethyl, sethoxydim, and BAS-517-H, but was controlled by recommended field rates for these herbicides. The mechanism of resistance was investigated for diclofop-methyl. There was little or no difference in diclofop-methyl absorption by leaves of resistant and susceptible biotypes measured 48 h after treatment. For both biotypes, less than 1% of absorbed radiolabel was translocated during 48 h following foliar application of 14C-diclofop-methyl. Metabolism of diclofop-methyl was not significantly altered in the resistant biotype. In both biotypes, diclofop-methyl was rapidly metabolized to diclofop acid followed by a slow rate of formation of a polar conjugate. Two multifunctional acetyl coenzyme A carboxylase isoforms (ACCase I and ACCase II) were isolated from leaf tissue of resistant and susceptible biotypes. Both isoforms exhibited a subunit molecular mass of 203 kDa. For both resistant and susceptible biotypes, ACCase I constituted approximately 80% of total ACCase activity. Graminicide concentrations required to inhibit ACCase activity by 50% (I50 values) were determined for both ACCase isoforms from resistant and susceptible biotypes. The ACCase II isoform was highly resistant to graminicides in both biotypes. In contrast, the I50 value for diclofop inhibition of ACCase I was 19-fold greater for the enzyme isolated from the resistant biotype compared with the susceptible biotype. It is concluded that diclofop resistance in the L. multiflorum biotype from Normandy is caused by the presence of a resistant form of the ACCase I isoform.

Greenhouse and laboratory experiments were conducted to investigate the response of winter wheat, and two diclofop-methyl–sensitive (OR and KG) and four diclofop-methyl–resistant (EP, GT, RBG, and JB) Italian ryegrass biotypes to the experimental herbicide mixture AE F130060 03 (an 8.3:1.7 mixture of the experimental sulfonylurea herbicides AE F130060 00 and AE F115008 00). AE F130060 03 at 15 or 18 g ha−1 without the safener AE F107892 reduced biomass of winter wheat 10 to 14%, whereas applications made with AE F107892 did not reduce wheat biomass. AE F130060 03 at 15 or 18 g ai ha−1 was more effective than diclofop-methyl in reducing biomass of one diclofop-methyl–sensitive Italian ryegrass biotype and all four diclofop-methyl–resistant biotypes. However, differential responses to AE F130060 03 at 15 and 18 g ha−1 occurred among diclofop-methyl–resistant biotypes. AE F130060 03 at 15 or 18 g ha−1 reduced biomass of OR, KG, EP, and GT from 61 to 84% but reduced biomass of RBG and JB biotypes only 35 to 52%. Absorption, translocation, and metabolism experiments were conducted to further investigate differential response of diclofop-methyl–sensitive KG and diclofop-methyl–resistant JB to AE F130060 00. Absorption, translocation, and metabolism of AE F130060 00 in winter wheat treated with or without the herbicide safener AE F107892 were also included for comparison. Foliar absorption of [14C]AE F130060 00 was influenced only by plant species because Italian ryegrass biotypes absorbed at least three times more AE F130060 00 than did wheat 12, 36, and 72 h after treatment (HAT). No more than 9% of absorbed radioactivity translocated into shoots and roots of either species during the experiment. Greatest overall metabolism occurred in winter wheat treated with the safener AE F107892. Seventy-two HAT, relative amounts of parent AE F130060 00 in Italian ryegrass biotypes were nearly 1.8 times greater than that in wheat that received AE F107892 and nearly 1.5 times greater than that in unsafened wheat. However, obvious differences in herbicide metabolism between diclofop-methyl–sensitive KG and diclofop-methyl–resistant JB were not evident. We hypothesize that differential sensitivity to AE F130060 00 in these biotypes is most likely due to a less sensitive acetolactate synthase, although further research is required to confirm this hypothesis.

Laboratory experiments were conducted to evaluate absorption, translocation, and metabolism of AE F130060 03 in wheat, barley, and Italian ryegrass. An additional objective was to evaluate how combinations of AE F130060 03 with dicamba affect absorption, translocation, and metabolism in wheat, barley, and Italian ryegrass. Experiments were conducted in a completely randomized design, and data were subjected to a factorial analysis. The factors included for analysis were plant type, time, and presence or absence of dicamba. Italian ryegrass absorbed 2.5, 2.0, and 1.5 times the amount of applied radioactivity 24, 48, and 96 h after treatment (HAT), respectively, compared with wheat or barley. Translocation of radiolabeled AE F130060 03 from the treated leaf blade was low and did not differ among wheat, barley, or Italian ryegrass. The rates of AE F130060 03 metabolism by the two cereal crops and Italian ryegrass were different. Ninety-six HAT, the total absorbed radioactivity metabolized by wheat, barley, and Italian ryegrass was 67, 51, and 34%, respectively. Conversely, 96 HAT, the levels of nonmetabolized AE F130060 03 were highest in Italian ryegrass, intermediate in barley, and lowest in wheat. The lower absorption of herbicide and a more rapid rate of metabolism by wheat and barley in comparison with Italian ryegrass most likely account for differential selectivity among the three plant species. Dicamba did not influence translocation or metabolism in wheat, barley, or Italian ryegrass.

The biochemical basis of resistance to the acetyl-coenzyme A carboxylase (ACCase)-inhibiting herbicide diclofop-methyl was investigated in a resistant wild oat population (R1), which does not exhibit a resistant ACCase. Rates of foliar uptake and translocation of [14C]-diclofop were the same in the R1 vs. susceptible (S) populations. However, the level of phytotoxic diclofop acid was always found to be lower in the R1 vs. S plants, with a concomitant higher level (up to 1.7-fold) of nontoxic polar diclofop metabolites in R1 relative to the S plants. These results indicate that a non–target-site-based mechanism of enhanced rate of diclofop acid metabolism confers resistance in population R1. Moreover, the high-performance liquid chromotography elution profile of the major diclofop metabolites in R1 is similar to that of wheat, suggesting resistance in individuals of population R1 involves a wheat-like detoxification system mediated by cytochrome P450 monooxygenases. In addition, lower level of tissue diclofop acid was also observed using nonradioactive ultra-performance liquid chromatography–mass spectrometry analysis in resistant individuals of three other resistant wild oat populations (R2, R3, and R4) known to posses ACCase gene resistance mutations. These results establish that either one or at least two independent resistance mechanisms (target-site ACCase resistance mutations and non–target-site enhanced rates of herbicide metabolism) can be present in individual wild oat plants.

Herbicide resistance in rigid ryegrass is an escalating problem in grain-cropping fields of southeastern Australia due to increased reliance on herbicides as the main method for weed control. Weed surveys were conducted between 1998 and 2009 to identify the extent of herbicide-resistant rigid ryegrass across this region to dinitroaniline, and acetolactate synthase- and acetyl coenzyme A (CoA) carboxylase-inhibiting herbicides. Rigid ryegrass was collected from cropped fields chosen at random. Outdoor pot studies were conducted during the normal winter growing season for rigid ryegrass with PRE-applied trifluralin and POST-applied diclofop-methyl, chlorsulfuron, tralkoxydim, pinoxaden, and clethodim. Herbicide resistance to trifluralin in rigid ryegrass was identified in one-third of the fields surveyed from South Australia, whereas less than 5% of fields in Victoria exhibited resistance. In contrast, resistance to chlorsulfuron was detected in at least half of the cropped fields across southeastern Australia. Resistance to the cereal-selective aryloxyphenoxypropionate-inhibiting herbicides diclofop-methyl, tralkoxydim, and pinoxaden ranged between 30 and 60% in most regions, whereas in marginal cropping areas less than 12% of fields exhibited resistance. Resistance to clethodim varied between 0 and 61%. Higher levels of resistance to clethodim were identified in the more intensively cropped, higher-rainfall districts where pulse and canola crops are common. These weed surveys demonstrated that a high incidence of resistance to most tested herbicides was present in rigid ryegrass from cropped fields in southeastern Australia, which presents a major challenge for crop producers.

A random survey of 264 cropping fields in the Western Australian wheat belt was conducted to determine the extent of rigid ryegrass resistance to commonly used acetolactate synthase- and acetyl-CoA carboxylase-inhibiting herbicides. Rigid ryegrass infestation density was assessed and seed samples collected and subsequently tested for resistance to diclofop-methyl, clethodim, chlorsulfuron, and sulfometuron. Of these randomly collected populations, 46% exhibited resistance to diclofop-methyl and 64% to chlorsulfuron, with 37% exhibiting multiple resistance to both herbicides. Only 28% of tested populations were classified as susceptible to both diclofop-methyl and chlorsulfuron, although all but one population were susceptible to clethodim. Large differences in the proportion of fields containing resistant populations were found between agronomic areas, reflecting different cropping and, therefore, herbicide use history. There was no significant association between resistance status and the density at which rigid ryegrass was present. Herbicide-resistant rigid ryegrass populations are now more common than susceptible populations across much of the Western Australian wheat belt.

Herbicide-resistant weeds are a constraint to weed management in many cropping regions around the world. Of the numerous populations of weeds with resistance to herbicides, it appears that most have resistance due to an alteration to the target enzyme. Use of herbicides with alternative modes of action has relatively easily controlled these populations. In stark contrast are a much smaller number of populations with resistance due to increased rates of herbicide detoxification. These populations may be cross-resistant to herbicides with other modes of action. Such cross-resistance can severely compromise weed control because alternative herbicides may fail on their first use. It has proved extremely difficult to predict cross-resistance due to increased herbicide detoxification in weed populations and hence, difficult to provide adequate advice to growers on how to avoid or manage the problem. Most commonly, such cross-resistance has been selected by certain aryloxyphenoxypropanoate herbicides such as diclofop-methyl and phenylurea herbicides such as chlorotoluron and isoproturon; however, other herbicides can also act as selecting agents for this type of resistance. Illustrative examples from rigid ryegrass in Australia and blackgrass in Europe demonstrate the breadth of the problem and the magnitude of the effort required to understand increased herbicide detoxification as a resistance mechanism. Recent work has elucidated the genetic basis of cross-resistance in some populations, but this has so far not provided new predictive tools useful to growers. Despite more than a decade of research aimed at unraveling the complexities of cross-resistance due to increased herbicide detoxification, management of these cross-resistant populations remains a significant challenge.

Field experiments were conducted in Virginia in 2000 and 2001 to determine the response of wheat and Italian ryegrass biotypes to postemergence applications of diclofop-methyl compared with several experimental and registered herbicides. Control of diclofop-methyl–sensitive Italian ryegrass by AE F130060 03 was similar to control by diclofop-methyl and was greater than that by chlorsulfuron plus metsulfuron, chlorsulfuron plus metribuzin, MON 37560, ICIA 0604, and CGA 184927. AE F130060 03 also controlled diclofop-methyl–resistant Italian ryegrass better than the other herbicides. Late-season spike density of diclofop-methyl–resistant Italian ryegrass was reduced 91 to 98% by AE F130060 03. Despite injury ranging from 10 to 24%, grain yield from wheat treated with AE F130060 03 was similar to or greater than yield from wheat treated with the other herbicides. Italian ryegrass control, spike density, and grain yield were not influenced by AE F130060 03 rate or addition of methylated seed oil.