Related Herbicides Research Articles

Preparation of a Pyrazosulfuron-Ethyl Imprinted Polymer with Hydrophilic External Layers by Reversible Addition-Fragmentation Chain Transfer Precipitation and Grafting Polymerization

A new imprinted polymer with both functions of molecular recognition and macromolecule exclusion was synthesized for selective extraction of pyrazosulfuron-ethyl and removal of humic acids in environmental analysis. In the preparation, spherical pyrazosulfuron-ethyl imprinted polymers were synthesized by reversible addition–fragmentation chain transfer (RAFT) precipitation polymerization. The hydrophilic polymer layers were then grafted on the surface of the imprinted polymer microspheres using post-RAFT polymerization. The conditions that influence the selectivity, size, and uniformity of the imprinted microspheres were studied systematically. The computer simulation was employed to study the template-monomer interaction. The solubility parameters of poly(MAA-co-EDMA) and porogen were calculated to investigate the relationship between the particle size and the solubility parameter. The results indicated that the pyrazosulfuron-ethyl imprinted polymers have special affinity for the template and several structurally related sulfonylurea herbicides. The molecularly imprinted polymer (MIP) with external hydrophilic chains not only had function of template retention, but also better function of protein/humic acid exclusion. This research demonstrates that multifunctional imprinted material with a narrow size distribution can be prepared by the RAFT polymerization.

Occurrence and Distribution of Sulfonylurea and Related Herbicides in Central Canadian Surface Waters 2006–2008

Surface water sampling in 2006-2008 measured the occurrence of sulfonylureas and related herbicides (SUs) during base flow conditions and wet weather events. Flumetsulam (29.2%), diuron (36.5%) and fomesafen (25.3%) were most frequently detected over the course of the study. Typical SU concentrations were in the low parts per trillion range; however, maximum concentrations of fomesafen (873 ng/L), linuron (856 ng/L) and diuron (2,900 ng/L) approached or exceeded 1 μg/L. The temporal trend in SUs showed a correlation with application periods. In general, detections of SUs were more frequent where rotation of row crops was more intense. Sampling during wet-weather events indicated potential for a range of SUs to be flushed into surface waters at relatively high concentrations.

Catalase activity as a potential vital biomarker of fish intoxication by the herbicide aminotriazole

The objective of this study was to investigate the effects of the herbicide 3-amino-1,2,4-triazole (AMT) on the activities of catalase and lactate dehydrogenase (LDH) in blood (plasma and erythrocytes) and eight solid tissues of goldfish, Carassius auratus. Injection of goldfish with AMT (0.5 mg/gww AMT in 0.9% NaCl) resulted in a significant decrease in catalase activity 24 h post-injection in most tissues investigated. In white and red muscle, kidney, heart, liver, brain and erythrocytes the activity of catalase decreased by 61%, 69%, 64%, 48%, 40%, 27% and 26%, respectively, in comparison to the values seen in animals injected with physiological saline (0.9% NaCl). However, the activity of LDH decreased only in red muscle (by 19%) after AMT injection, whereas in plasma it increased by 137%. Protein carbonyl levels, a measure of oxidative damage to proteins, did not change in plasma in goldfish injected with AMT and total hemoglobin levels in AMT-injected fish, although lower compared with uninjected controls, did not differ from values in saline-injected controls. It is proposed that catalase activity in erythrocytes and white muscle might be usefully developed as a potential marker for fish intoxication by aminotriazole and other related herbicides.

Herbicide Transport in Goodwater Creek Experimental Watershed: II. Long-Term Research on Acetochlor, Alachlor, Metolachlor, and Metribuzin1

Lerch, R.N., E.J. Sadler, C. Baffaut, N.R. Kitchen, and K.A. Sudduth, 2010. Herbicide Transport in Goodwater Creek Experimental Watershed: II. Long-Term Research on Acetochlor, Alachlor, Metolachlor, and Metribuzin. Journal of the American Water Resources Association (JAWRA) 1-15. DOI: 10.1111/j.1752-1688.2010.00504.x Abstract: Farmers in the Midwestern United States continue to be reliant on soil-applied herbicides for weed control in crop production, and herbicide contamination of streams remains an environmental problem. The main objective of this study was to analyze trends in concentration and load of acetochlor, alachlor, metolachlor, and metribuzin in Goodwater Creek Experimental Watershed (GCEW) from 1992 to 2006. A secondary objective was to document the effects of best management practices (BMPs) implemented within GCEW on herbicide transport trends. Median relative herbicide loads, as a percent of applied, were 3.7% for metolachlor, 1.3% for metribuzin, 0.36% for acetochlor, and 0.18% for alachlor. The major decrease in alachlor use and increase in acetochlor use caused shifts in flow-weighted concentrations that were observed over the entire concentration range. The smaller decrease in metolachlor use led to a consistent decreasing time trend only for the upper end of the concentration distribution. Metribuzin also showed moderate decreases in concentration with time since 1998. Annual loads were generally correlated to second quarter discharge. Despite extensive education efforts in the watershed, conservation BMPs within GCEW were mainly implemented to control erosion, and therefore had no discernable impact on reducing herbicide transport. Overall, changes in herbicide use and second quarter discharge had the greatest effect on trends in flow-weighted concentration and annual load.

Herbicide tolerant canola systems and their impact on winter crop rotations

Canola is widely grown in Australia to provide diversity within winter crop rotations. Its production is heavily reliant on triazine tolerant varieties but Clearfield ® and conventional varieties are also significant components of the industry. Glyphosate tolerant varieties have been introduced, thereby providing an alternative technology to be incorporated into the farming systems. To evaluate the potential impact of the relative herbicide technologies, a comparison of herbicide tolerant canola weed management systems was undertaken at Wagga Wagga, Australia over a 5-year rotation. Near isogenic lines of conventional, glyphosate tolerant and triazine tolerant varieties were evaluated for their abilities to control annual ryegrass ( Lolium rigidum), the most challenging weed of temperate crops in Australia. Glyphosate tolerant and triazine tolerant canola achieved high levels of ryegrass control and attained higher yields than the conventional system. Glyphosate tolerant canola provided extra control of broadleaf weeds and also achieved better seed oil levels when compared with the other canola systems. There were positive flow-on weed management benefits for the remainder of the crop sequence from the weed control achieved in the initial crop, particularly following glyphosate tolerant canola. Subsequent control of volunteer canola in all treatments was readily achieved by using paraquat/diquat. The glyphosate tolerant weed management system was more profitable than the triazine tolerant system, although no allowance was made for technology costs as they were not known at the time of study. These outcomes demonstrate the potential value of herbicide tolerant canola to Australian farmers.

Comparison of 16S rRNA gene phylogeny and functional tfdA gene distribution in thirty-one different 2,4-dichlorophenoxyacetic acid and 4-chloro-2-methylphenoxyacetic acid degraders

31 different bacterial strains isolated using the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) as the sole source of carbon, were investigated for their ability to mineralize 2,4-D and the related herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA). Most of the strains mineralize 2,4-D considerably faster than MCPA. Three novel primer sets were developed enabling amplification of full-length coding sequences (CDS) of the three known tfdA gene classes known to be involved in phenoxy acid degradation. 16S rRNA genes were also sequenced; and in order to investigate possible linkage between tfdA gene classes and bacterial species, tfdA and 16S rRNA gene phylogeny was compared. Three distinctly different classes of tfdA genes were observed, with class I tfdA sequences further partitioned into the two sub-classes I-a and I-b based on more subtle differences. Comparison of phylogenies derived from 16S rRNA gene sequences and tfdA gene sequences revealed that most class II tfdA genes were encoded by Burkholderia sp., while class I-a, I-b and III genes were found in a more diverse array of bacteria.

Brain Toxicokinetics of Prometryne in Mice

Prometryne is a methylthio-s-triazine herbicide. Significant trace amounts are found in the environment, mainly in water, soil, and food plants. The aim of this study was to establish brain and blood prometryne levels after single oral dose (1 g kg-1) in adult male and female mice. Prometryne was measured using the GC/MS assay at 1, 2, 4, 8, and 24 h after prometryne administration. Peak brain and blood prometryne values were observed 1 h after administration and they decreased in a time-dependent manner. Male mice had consistently higher brain and blood prometryne levels than female mice. The observed prometryne kinetics was similar to that reported for the structurally related herbicide atrazine.

A composite transcriptional signature differentiates responses towards closely related herbicides in Arabidopsis thaliana and Brassica napus

In this study, genome-wide expression profiling based on Affymetrix ATH1 arrays was used to identify discriminating responses of Arabidopsis thaliana to five herbicides, which contain active ingredients targeting two different branches of amino acid biosynthesis. One herbicide contained glyphosate, which targets 5-enolpyruvylshikimate-3-phosphate synthase (EPSPS), while the other four herbicides contain different acetolactate synthase (ALS) inhibiting compounds. In contrast to the herbicide containing glyphosate, which affected only a few transcripts, many effects of the ALS inhibiting herbicides were revealed based on transcriptional changes related to ribosome biogenesis and translation, secondary metabolism, cell wall modification and growth. The expression pattern of a set of 101 genes provided a specific, composite signature that was distinct from other major stress responses and differentiated among herbicides targeting the same enzyme (ALS) or containing the same chemical class of active ingredient (sulfonylurea). A set of homologous genes could be identified in Brassica napus that exhibited a similar expression pattern and correctly distinguished exposure to the five herbicides. Our results show the ability of a limited number of genes to classify and differentiate responses to closely related herbicides in A. thaliana and B. napus and the transferability of a complex transcriptional signature across species.Electronic supplementary materialThe online version of this article (doi:10.1007/s11103-009-9590-y) contains supplementary material, which is available to authorized users.

Misturas de herbicidas com adubo molíbdico na cultura do feijão

Foram conduzidos dois experimentos em Coimbra-MG no período de março a julho, em anos consecutivos, com o objetivo de avaliar possível interação proporcionada pela mistura de adubo molíbdico com herbicidas em relação à produtividade e ao controle de plantas daninhas na cultura do feijão, cv. Meia Noite. O delineamento experimental foi o de blocos ao acaso, com quatro repetições, tendo as parcelas subdivididas. As parcelas foram representadas pela ausência e presença de capina, e as subparcelas, pelos tratamentos com os herbicidas metolachlor, fomesafen, bentazon, imazamox e fluazifop-p-butil + fomesafen e pela testemunha com capina, associados ou não ao molibdênio. Este micronutriente foi aplicado na dosagem de 80 g ha-1, aos 23 dias após a emergência da cultura, em mistura no tanque com os herbicidas aplicados em pós-emergência e isoladamente, quando o herbicida foi aplicado apenas em pré-emergência e nas testemunhas. Utilizou-se como fonte de molibdênio o molibdato de amônio. O molibdênio pode ser misturado aos herbicidas estudados e, mesmo assim, proporcionar aumento na produtividade; os herbicidas metolachlor + fomesafen, metolachlor + bentazon, fluazifop-p-butil + fomesafen e imazamox apresentaram de muito bom a ótimo controle de Ipomoea grandifolia, Brachiaria plantaginea e Acanthospermum hispidum. Não houve redução no controle das espécies daninhas presentes em ambos os experimentos quando o molibdênio foi misturado à calda.

Environmental Analysis by On-Line Immunoextraction and Reversed-Phase Liquid Chromatography: Optimization of the Immunoextraction/RPLC Interface

The use of antibodies in HPLC columns for on-line immunoextraction combined with reversed-phase liquid chromatography (RPLC) is of growing interest in environmental and agricultural analysis. This technique is typically performed by using a small RPLC precolumn to capture and concentrate analytes as they elute from the immunoextraction column; however, there is little information on the conditions required for optimizing this interface. This study examined the behavior of this interface by using 2,4-dichlorophenoxyacetic acid (2,4-D) and related herbicides as model analytes. It was found that analyte dissociation from immunoextraction columns followed first-order decay and that the elution of these analytes through the immunoextraction/RPLC interface gave an exponentially modified Gaussian profile. Computer simulations were used to see how analyte elution through the interface changed with different dissociation and retention conditions. Several guidelines were developed from this work that could be used for developing and optimizing on-line immunoextraction/RPLC systems for other chemicals of environmental or agricultural interest.

Compliance analysis of phenylurea and related compounds in drinking water by liquid chromatography/electrospray ionization/mass spectrometry coupled with solid-phase extraction

A liquid chromatography/electrospray ionization/mass spectrometry method was reported for the compliance analysis of seven phenylurea compounds and two related herbicides (tebuthiuron and propanil) in drinking water. The volumes of the sample and final extract used in the method were 500 mL and 10 mL, respectively. The obtained method detection limits were less than 0.03 μg/L, and the mean recoveries were 74–128% with a relative standard deviation of 2.6–8.3% for all the studied compounds. The peak-to-peak signal-to-noise ratios ranged from 3.3 for cis-siduron to 34.2 for fluometuron. The accuracy and precision resulting from reagent and drinking water samples fortified at higher concentration levels were similar to these results. Several analytes were detected in the drinking water samples, including tebuthiuron at 0.5 μg/L, propanil at 0.7 μg/L, diuron at 0.1–2.1 μg/L, and linuron at 0.1–0.8 μg/L.

Glyphosate Immunosensor. Application for Water and Soil Analysis

A fully automated immunosensor for the herbicide glyphosate has been developed on the basis of the immunocomplex capture assay protocol. The sensor carries out on-line analyte derivatization prior to the assay and uses a selective anti-glyphosate serum, a glyphosate peroxidase enzyme tracer, and fluorescent detection. Under optimal conditions, the detection limit achieved is 0.021 microg/L with an analysis rate of 25 min per assay, autonomy of more than 48 h, and sensor reusability >500 analytical cycles. The immunosensor is able to discriminate structurally related molecules, such as aminomethylphosphonic acid, the main metabolite of glyphosate, and other related herbicides, such as glufosinate and glyphosine. Interferences from naturally occurring species (anions, cations, and humic substances) and their elimination were also studied. The immunosensor has been successfully applied to water and soil sample analysis, with good recoveries at levels lower than 1 microg/L. Results obtained with the immunosensor correlate well with data from a magnetic particle ELISA and LC/LC/MS chromatographic method.

RETRACTION

Asparagine (Asn) synthetase (AS) is the key enzyme in Asn biosynthesis and plays an important role in nitrogen mobilization. Despite its important physiological function, little research has been done documenting inhibitors of plant AS. Plant growth inhibition caused by the natural monoterpene 1,4-cineole and its structurally related herbicide cinmethylin was reversed 65% and 55%, respectively, by providing 100 μm Asn exogenously. Reversion of the phytotoxic effect was dependent on the concentration of Asn. The presence of either 1,4-cineole or cinmethylin stimulated root uptake of [14C]Asn by lettuce (Lactuca sativa) seedlings. Although the physiological responses suggested that both compounds affected Asn biosynthesis, biochemical analysis of AS activity showed that the natural monoterpene was a potent inhibitor (I50 = approximately 0.5 μm) of the enzyme, whereas the commercial product was not inhibitory up to levels of 10 mm. Analysis of the putative metabolite, 2-hydroxy-1,4-cineole, showed that the cis-enantiomer was much more active than the trans-enantiomer, suggesting that the hydroxyl group was involved in the specific ligand/active site interaction. This is the first report that AS is a suitable herbicide target site, and that cinmethylin is apparently a proherbicide that requires metabolic bioactivation via cleavage of the benzyl-ether side chain.

Development and Characterization of an Immunoaffinity Solid-Phase-Extraction Sorbent for Trace Analysis of Propanil and Related Phenylurea Herbicides in Environmental Waters and in Beverages

An immunoaffinity solid-phase-extraction sorbent has been developed by raising polyclonal antibodies against propanil and covalently bonding them to activated silica. This immunosorbent (IS) had high affinity for propanil and for structurally related phenylurea herbicides whereas structurally related chloroanilines were retained only poorly. Studies of breakthrough volumes, capacity, and calibration ranges of selected pesticides showed that the antibodies have different affinities for each compound. Propanil and phenylureas could be quantitatively recovered by elution with methanol–water; average recoveries were close to 100%. The IS was also packed in a precolumn and coupled on-line to HPLC–UV. The high selectivity provided by the IS was demonstrated by comparing results with those obtained by use of a non-selective polymeric sorbent when both were used for direct extraction of propanil and phenylureas from a 50-mL sample of river-Seine water spiked at 0.1 μg L−1 or from lemon juice spiked at 50 μg L−1.

Experimental hepatic uroporphyria induced by the diphenyl-ether herbicide fomesafen in male DBA/2 mice

Hepatic uroporphyria can be readily induced by a variety of treatments in mice of the C57BL strains, whereas DBA/2 mice are almost completely resistant. However, feeding of the protoporphyrinogen oxidase-inhibiting herbicide fomesafen (0.25% in the diet for 18 weeks) induced hepatic uroporphyria in male DBA/2N mice (liver porphyrin content up to 150 nmol/g, control animals 1 nmol/g), whereas fomesafen-treated male C57BL/6N mice displayed only a slight elevation of liver porphyrins (∼5 nmol/g). The profile of accumulated hepatic porphyrins in fomesafen-treated DBA/2N mice resembled the well-characterised uroporphyria induced by polyhalogenated aromatic hydrocarbons, while histological examination confirmed the presence of uroporphyria-specific cytoplasmic inclusions in the hepatocytes. Uroporphyrinogen decarboxylase activity decreased to about 30% of control values in fomesafen-treated DBA/2N mice; microsomal methoxyresorufin O-dealkylase activity was slightly reduced. The amount of CYP1A1 and CYP1A2 mRNA, as determined by real-time PCR, was not significantly changed; mRNA encoding the housekeeping 5-aminolevulinic acid synthase was elevated 10-fold. Total liver iron was slightly increased. A similar uroporphyria was induced by the herbicide formulation Blazer, containing a structurally related herbicide acifluorfen, when fed to DBA/2N mice at a dose corresponding to 0.25% of acifluorfen in the diet. Since DBA/2 mice are almost completely resistant to all well-characterised porphyrogenic chemicals, the results suggest the possible existence of a yet unknown mechanism of uroporphyria induction, to which the DBA/2 mouse strain is more sensitive than the C57BL strain.

Injury to Landscape and Vegetable Plants by Volatile Turf Herbicides

Phenoxy and related herbicides used in turfgrass have the potential for volatilization and movement from treated areas. Three studies assessed potential injury to subtropical landscape plants caused by volatile turf herbicides in polyethylene enclosures. Phenoxy herbicide mixtures were emphasized. There were significant differences among the seven landscape species tested. The most sensitive species were african marigold (Tagetes erecta), joseph's coat (Alternanthera ficoidea), and tomato (Lycopersicon esculentum). Severe injury was caused by exposure to herbicides containing 2,4-D isooctyl ester and MCPA isooctyl ester. Exposure to individual active ingredients 2,4-D dimethylamine, dicamba acid, atrazine, and metsulfuron resulted in no injury to the species tested.

Studies of Spray Application of Microbial Herbicides in Relation to Conidial Propagule Content of Spray Droplets and Retention on Target

This paper addresses the hypothesis that the spray application system used will affect the retention of spray deposits of microbial herbicides on different plant structures. There was greater spray retention on the hypocotyl of 4 to 6-true leaf Amaranthus retroflexus plants (20-31%) sprayed with an aerosol-producing laboratory sprayer than with a hydraulic nozzle (3-5%). Spray deposition and retention from the hydraulic nozzle was increased by 28-42% when the nozzle was used horizontally. Spray droplets generally contained the expected conidial number for the conidial concentration but this was affected by increased inoculum density (size, concentration and mycelial contamination), causing a reduction in the actual number of conidia present, compared to the expected. Up to 40-50% of the conidia in the sprayed suspension could not be accounted for when conidium deposition was on a target. This loss could increase to 90-92% when the weed was sprayed under a crop canopy.

Herbicide efficacy, leaf structure, and spray droplet contact angle amongIpomoeaspecies and smallflower morningglory

Abstract Greenhouse and laboratory studies were conducted to evaluate responses of ivyleaf morningglory, pitted morningglory, palmleaf morningglory, and smallflower morningglory to several herbicides in relation to leaf structure, epicuticular wax, and spray droplet behavior. Two- to four-leaf stage plants of each species were highly susceptible to acifluorfen, bentazon, bromoxynil, glufosinate, and glyphosate. However, at the five- to eight-leaf stage, these species were less susceptible, and control was herbicide specific. Spray droplets of these five herbicides had a higher contact angle on ivyleaf morningglory than the other three species with a few exceptions. Stomata and glands were present on both adaxial and abaxial leaf surfaces of all species, and palmleaf morningglory and smallflower morningglory had more of these than did the other two species. Trichomes were present on all species except palmleaf morningglory. Epicuticular wax mass was highest in ivyleaf morningglory (57 μg cm−2) and lowest i...

Molecularly imprinted solid-phase extraction sorbent for the clean-up of chlorinated phenoxyacids from aqueous samples

A molecularly imprinted polymer (MIP) was synthesized using the herbicide 2,4,5-trichlorophenoxyacetic acid as a template, 4-vinylpyridine as an interacting monomer, ethylendimethacrylate as a cross-linker and a methanol–water mixture as a porogen. The binding properties and the selectivity of the polymer towards the template were investigated by frontal and zonal liquid chromatography. The polymer was used as a solid-phase extraction material for the clean-up of the template molecule and some related herbicides (2,4-dichlorophenoxyacetic acid, fenoprop, dichlorprop) from river water samples at a concentration level of ng/ml with quantitative recoveries comparable with those obtained with a traditional C 18 reversed-phase column when analyzed by capillary electrophoresis. The results obtained show that the MIP-based approach to the solid-phase extraction is comparable with the more traditional solid-phase extraction with C 18 reversed-phase columns in terms of recovery, but it is superior in terms of sample clean-up.

Comparison of the performance of bromoxynil-resistant and susceptible near-isogenic populations of oilseed rape

Bromoxynil herbicide resistance is the newest type of broad-spectrum, non-selective herbicide resistance to be introduced into oilseed rape (Brassica napus L.). This herbicide resistance is conferred by a single transgene (the oxy gene), taken from a soil bacterium, which confers the ability to metabolize hydroxybenzonitrile herbicides such as bromoxynil. The level of resistance to bromoxynil herbicide in oilseed rape is high, but it is not known whether there are any performance changes associated with the oxy transgene or with the derived herbicide resistance. To determine if there are changes in performance related to the oxy transgene, or the derived herbicide resistance, two near-isogenic transgenic bromoxynil-resistant populations, with two different forms of the oxy gene, Westar 235 and Westar 237, were developed at the University of Manitoba, grown in the field in Manitoba for several years and evaluated for comparative performance. Westar 235 and Westar 237 near-isogenic populations, either sprayed with bromoxynil at 280 g a.i. ha–1 or left unsprayed, were compared with the non-transgenic near-isogenic population cultivar, Westar, in Winnipeg, Carman, and Portage la Prairie from 1994 to 1997. There were no consistent differences in the performance of the sprayed or unsprayed transgenic near-isogenic populations in comparison to Westar for any trait. The few significant and minimal differences that were found were evenly divided between positive effects and negative effects of the oxy gene and derived herbicide resistance. There were no significant effects of spraying bromoxynil herbicide detected in paired comparisons of Westar 235 and Westar 237 sprayed versus Westar 235 and Westar 237 unsprayed, respectively. The effects of the oxy transgenes and the effects of bromoxynil spraying of herbicide-resistant lines were negligible, indicating that there is little, if any biological cost associated with the bromoxynil resistance transgenes or related herbicide resistance. Key words: Transgenic oilseed rape, Brassica napus, biological cost