clay and metolachlor

The environmental effects of safeners, agrochemicals that protect crops from herbicide toxicity, are largely unknown, perhaps because they are classified as inert ingredients. We assessed the toxicity to larvae of Chironomus riparius of 1) the dichloroacetamide safener benoxacor; 2) its degradation product, monochloro-benoxacor; 3) the herbicide with which benoxacor is paired, S-metolachlor; and 4) a mixture of S-metolachlor + benoxacor. Under iron-reducing conditions, benoxacor can undergo reductive dechlorination, producing monochloro-benoxacor. To simulate iron-reducing conditions, we prepared benthic microcosms containing an iron-rich silt-clay sediment amended with cellulose. Larval C. riparius were exposed to single chemicals via spiked sediment at nominal concentrations ranging from 0.01 to 100 mg/kg. Concentrations of a 1:1 mixture of safener and herbicide ranged from 0.02 to 200 mg/kg. Kinetic modeling of microcosm aqueous-phase concentrations indicated that benoxacor transformed with a half-life of 12 d. Cox proportional hazard models of time to emergence during 28-d experiments showed that females had a lowest-observed-effect concentration (LOEC) for benoxacor at 1 mg/kg, whereas their LOEC for monochloro-benoxacor was 0.1 mg/kg. For males, the LOEC for all treatments was 100 mg/kg (200 mg/kg for the mixture). Synergistic effects of the mixture were observed only in females, with a LOEC of 0.2 mg/kg. These results suggest that benoxacor presents a low toxicity risk to C. riparius in environmental systems; however, the possibility of synergistic effects between benoxacor and S-metolachlor merits further investigation. Environ Toxicol Chem 2017;36:2660-2670. © 2017 SETAC.

Topics: Acetamides; Aluminum Silicates; Animals; Behavior, Animal; Chironomidae; Clay; Drug Synergism; Female; Half-Life; Herbicides; Larva; Male; Oxazines; Proportional Hazards Models; Sex Factors; Toxicity Tests

An extensive four-year research program has been carried out to explore and acquire knowledge about the fundamental agricultural practices and processes affecting the mobility and bioavailability of pesticides in soils under semi-arid Mediterranean conditions. Pesticide leaching was studied under field conditions at five different depths using suction cups. Monitoring of metolachlor, alachlor, atrazine, deethylatrazine (DEA), deisopropylatrazine (DIA), and bromide ions in soil water, as well as dye patterns made apparent the significant role of preferential flow to the mobility of the studied compounds. Irrespective to their adsorption capacities and degradation rates, atrazine, metolachlor and bromide ions were simultaneously detected to 160 cm depth. Following 40 mm irrigation, just after their application, both alachlor and atrazine were leached to 160 cm depth within 18 h, giving maximum concentrations of 211 and 199 μg L(-1), respectively. Metolachlor was also detected in all depth when its application was followed by a rainfall event (50 mm) two weeks after its application. The greatest concentrations of atrazine, alachlor and metolachlor in soil water were 1795, 1166 and 845 μg L(-1), respectively. The greatest concentrations of atrazine's degradation products (both DEA and DIA) appeared later in the season compared to the parent compound. Metolachlor exhibited the greatest persistence with concentrations up to 10 μg L(-1) appearing in soil water 18 months after its application. Brilliant blue application followed by 40 mm irrigation clearly depict multi-branching network of preferential flow paths allowing the fast flow of the dye down to 150 cm within 24 h. This network was created by soil cracks caused by shrinking of dry soils, earthworms and plant roots. Chromatographic flow of the stained soil solution was evident only in the upper 10-15 cm of soil.

Topics: Acetamides; Agriculture; Aluminum Silicates; Atrazine; Bromides; Clay; Environmental Monitoring; Greece; Ions; Soil; Water Pollutants, Chemical

Use of genetically modified cultivars resistant to the herbicide glyphosate (N-phosphonomethylglycine) is strongly associated with conservation-tillage (CsT) management for maize ( Zea mays L.), soybean ( Glycine max L.), and cotton ( Gossypium hirsutum L.) cultivation. Due to the emergence of glyphosate-resistant weed biotypes, alternate weed management practices are needed to sustain CsT use. This work focused on metolachlor use (2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide) in a CsT system. The fate and efficacy of granular and emulsifiable concentrate (EC) formulations or an EC surrogate were compared for CsT cotton production in the Atlantic Coastal Plain region of southern Georgia (USA). The granular formulation, a clay-alginate polymer, was produced in the authors' laboratory; EC was a commercial product. In field and laboratory dissipations the granular metolachlor exhibited 8-fold greater soil persistence. Rainfall simulation runoff assessments indicated that use of the granular formulation in a common CsT system, strip-tillage (ST), may reduce metolachlor runoff loss when compared to conventional tillage (CT) management or when EC formulations are used in the ST system. Metolachlor leaching assessments using field-deployed lysimeters showed some tillage (ST > CT) and formulation (EC > granular) differences. Overall leaching was generally small when compared to runoff loss. Finally, greenhouse bioassays showed control of two weed species with the granular was greater than or equal to that of the EC formulation; however, the granular formulation suppressed cotton growth to a greater extent. In sum, this metolachlor granular formulation has advantages for CsT cotton production; however, additional research is needed to assess impacts on crop injury.

Topics: Acetamides; Agriculture; Alginates; Aluminum Silicates; Chromaffin Granules; Clay; Emulsions; Glucuronic Acid; Gossypium; Herbicides; Hexuronic Acids; Soil

Sulfentrazone and metolachlor have been detected in groundwater due to extensive leaching. To reduce herbicide leaching and increase weed control, we have developed, designed, and tested controlled release formulations (CRFs) for both herbicides based on their solubilizion in cationic micelles and adsorption of the mixed micelles (surfactant and herbicide) on a clay mineral, montmorillonite. A better understanding of solubilizing anionic (sulfentrazone) and nonionic (metolachlor) organic molecules in cationic micelles was reached. The percent of active ingredient in the formulations was much higher than previously designed CRFs due to the enhanced solubilization of the herbicides in the micelles and due to their adsorption on the clay. Both CRFs demonstrated controlled release (compared to the commercial formulations) when applied to a thin soil layer. A bioassay in soil columns determined that the new sulfentrazone and metolachlor CRFs significantly improve weed control and reduce leaching (for the latter) in comparison with the commercial formulations.

Topics: Acetamides; Adsorption; Aluminum Silicates; Cations; Clay; Delayed-Action Preparations; Herbicides; Kinetics; Micelles; Solubility; Sulfonamides; Triazoles

Adsorption of chloroacetanilide herbicides on homoionic montmorillonite was studied by coupling batch equilibration and FT-IR analysis. Adsorption decreased in the order metolachlor > acetochlor > alachlor > propachlor on Ca(2+)- or Mg(2+)-saturated clays and in the order metolachlor > alachlor > acetachlor > propachlor on Al(3+)- or Fe(3+)-saturated clays. FT-IR spectra showed that the carbonyl group of the herbicide molecule was involved in bonding. For the same herbicide, adsorption of alachlor, acetachlor, and metolachlor on clay followed the order Ca(2+) approximately Mg(2+) < Al(3+) < or = Fe(3+), which coincided with the increasing acidity of homoionic clays. Adsorption of propachlor, however, showed an opposite dependence, suggesting a different governing interaction. In clay and humic acid mixtures, herbicide adsorption was less than that expected from independent additive adsorption by the individual constituents, and the deviation was dependent on the clay-to-humic acid ratio, with the greatest deviation consistently occurring at a 60:40 clay-to-humic acid ratio.

Topics: Acetamides; Acetanilides; Adsorption; Aluminum; Aluminum Silicates; Calcium; Cations; Clay; Ferric Compounds; Herbicides; Humic Substances; Hydrogen-Ion Concentration; Magnesium; Soil; Spectroscopy, Fourier Transform Infrared; Toluidines

Metolachlor is a preplant, preemergent herbicide applied to corn and soybean fields. Agricultural runoff after application can cause the herbicide to enter into natural waters. The objective of this study was to determine the effect of river and wetland sediments on the toxicity of metolachlor. Sediments from a river and a wetland (separately) were mixed with Ottawa sand (0, 25, 50, 75, and 100%). Metolachlor (in water) and sediment were mixed in an orbital shaker for 8 hr; the mixture was centrifuged, and the supernatant liquid was tested for toxicity (EC50%) using the marine luminescent bacteria Vibrio fischeri (Microtox). The toxicity (EC50%) of metolachlor with the river sediment was 64.61. Metolachlor after interaction with the wetland sediment demonstrated no toxicity possibly due to increased adsorption on the higher amount of organic matter (10 times) and clay (3.5 times) present in the wetland sediment than the river sediment.

Topics: Acetamides; Aluminum Silicates; Clay; Fresh Water; Geologic Sediments; Herbicides; Luminescent Measurements; Photobacterium; Water Pollutants, Chemical