Aquatic exposure assessments for pesticides are generally based on laboratory studies performed in water alone or water sediment systems. Although aquatic macrophytes, which include a variety of bryophytes, macroalgae, and angiosperms, can be a significant component of many aquatic ecosystems, their impact on pesticide fate is generally not included in exposure assessments. To investigate the influence of aquatic plants on the fate and behavior of the pyrethroid insecticide lambda (lambda)-cyhalothrin, two laboratory experiments (to assess adsorption and degradation) and an indoor microcosm study (to assess fate under semirealistic conditions) were conducted. In the laboratory studies, adsorption to macrophytes was extensive and essentially irreversible, and degradation occurred rapidly by cleavage of the ester bond. In the indoor microcosm, which contained water, sediment, and macrophytes from a pond, degradation was also rapid, with DT50 and DT90 values of less than 3 and 19 h, respectively, for dissipation from the water column and of less than 3 and 56 h, respectively, for the whole system. For adsorptive and readily degraded pesticides like lambda-cyhalothrin, we conclude that macrophytes have considerable influence on fate and behavior in surface waters.
Experiments investigated irreversibility in pesticide sorption to soil. Sorption behaviour under abiotic conditions was quantified for chlorotoluron, prometryn and hexaconazole in three soils over periods of up to 274 days. An isotope-exchange procedure was used whereby sorption of (12)C- and (14)C-pesticide isotopes in shaken suspensions of three soils (56-168 days shaking) was followed by substitution of the isotopes in the liquid phase and a 14-day exchange phase. This was followed by forced isotope exchange where the sorbed (14)C material was exchanged by adding an excess of non-radiolabelled compound. Experiments were concluded with solvent extraction and soil combustion to determine remaining radioactivity. Under conditions of continuous shaking, the pesticide-soil systems took around four months to approach sorption equilibrium, resulting in strong asymmetry between the profiles of exchange for isotopes of all three compounds. Physically entrapped residues were released back into solution under the steep concentration gradient of forced isotope exchange and small amounts of radioactivity were still being released at the termination of the experiment. The profiles of exchange did not deviate markedly from ideal behaviour based on the assumption that sorption is fully reversible. Whilst the timescales for release of sorbed residues back into solution were very long, soil combustion at study termination only yielded <1-2% of applied radioactivity; this confirms that sorption processes under abiotic soil conditions were overwhelmingly reversible for this set of compounds and soils.
Aquatic exposure assessments for pesticides are generally based on laboratory studies performed in water alone or water sediment systems. Although aquatic macrophytes, which include a variety of bryophytes, macroalgae, and angiosperms, can be a significant component of many aquatic ecosystems, their impact on pesticide fate is generally not included in exposure assessments. To investigate the influence of aquatic plants on the fate and behavior of the pyrethroid insecticide lambda (lambda)-cyhalothrin, two laboratory experiments (to assess adsorption and degradation) and an indoor microcosm study (to assess fate under semirealistic conditions) were conducted. In the laboratory studies, adsorption to macrophytes was extensive and essentially irreversible, and degradation occurred rapidly by cleavage of the ester bond. In the indoor microcosm, which contained water, sediment, and macrophytes from a pond, degradation was also rapid, with DT50 and DT90 values of less than 3 and 19 h, respectively, for dissipation from the water column and of less than 3 and 56 h, respectively, for the whole system. For adsorptive and readily degraded pesticides like lambda-cyhalothrin, we conclude that macrophytes have considerable influence on fate and behavior in surface waters.
Soil surface photolysis can be a significant dissipation pathway for agrochemicals under field conditions, although it is assumed that such degradation ceases once the agrochemical is transported away from the surface following rainfall or irrigation and subsequent drainage of soil porewater. However, as both downward and upward water movements occur under field conditions, relatively mobile compounds may return to the surface, prolonging exposure to ultraviolet light and increasing the potential for degradation by photolysis. To test this hypothesis, a novel experimental system was used to quantify the contribution of photolysis to the overall dissipation of a new herbicide, bicyclopyrone, under conditions that mimicked field studies more closely than the standard laboratory test guidance. Soil cores were taken from 3 US field study sites, and the surfaces were treated with [(14) C]-bicyclopyrone. The radioactivity was redistributed throughout the cores using a simulated rainfall event, following which the cores were incubated under a xenon-arc lamp with continuous provision of moisture from below and a wind simulator to induce evaporation. After only 2 d, most of the test compound had returned to the soil surface. Significantly more degradation was observed in the irradiated samples than in a parallel dark control sample. Degradation rates were very similar to those observed in both the thin layer photolysis study and the field dissipation studies and significantly faster than in the soil metabolism studies conducted in the dark. Thus, for highly soluble, mobile agrochemicals, such as bicyclopyrone, photolysis is not terminated permanently by rainfall or irrigation but can resume following transport to the surface in evaporating water.
The metabolism of tralkoxydim was studied in wheat grown under field conditions and treated at a rate equivalent to 345 g a.i. ha −1. Maize plant cell suspension culture was used as a means of indicating the nature of the primary metabolic process, and also as a source of material for structural elucidation. The principal metabolic process in wheat involved hydroxylation of the p‐methyl function of the aromatic ring. This occurred in conjunction with a range of possible transformations of the (ethoxyimino)propyl function, or oxidative cleavage of the cyclohexanedione ring. All the initial metabolic products were amenable to further conjugation with a range of endogenous sugars.
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