Metabolism of 2,4-dichlorophenoxyacetic acid in laying hens and lactating goats

2,4-Dichlorophenoxyacetic acid (2,4-D) labeled with (14)C was found to be rapidly eliminated by laying hens and lactating goats dosed orally for 7 consecutive days at 18 mg/kg of food intake and for 3 consecutive days at 483 mg/kg of food intake, respectively. Excreta of hens and goats contained >90% of the total dose within 24 h after the final dose. Tissue residues were low and accounted for <0.1% of the dose in these animals. For hens, the residues in muscle, liver, and eggs (0.006-0.030 ppm) were lower than those found in fat and kidney (0.028-0.714 ppm), 2,4-D equivalents. The tissue with highest residue in goat was the kidney at 1.44 ppm, 2,4-D equivalents. Milk, liver, composite fat, and composite muscle had significantly lower residue levels of 0.202, 0.224, 0.088, and 0.037 ppm, respectively. The most abundant tissue residue was 2,4-D and acid/base releasable residues of 2,4-D. A minor metabolite was identified as 2,4-dichlorophenol.     

Fluorescent caged compounds of 2,4-dichlorophenoxyacetic acid (2,4-d): photorelease technology for controlled release of 2,4-D

A novel controlled-release formulation (CRF) of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) was developed to reduce its negative environmental impacts by improving its herbicidal efficacy. The 2,4-D was chemically caged by coupling with photoremovable protecting groups (PRPGs) of coumarin derivatives. Photophysical studies of caged compounds showed that they all exhibited strong fluorescence properties. Controlled release of 2,4-D was achieved by irradiating the caged compounds using UV-vis light (310, 350, and 410 nm). The effect of various factors such as pH, solvent, and different substituents at the seventh position of coumarin moiety on the rate of photorelease was studied. The herbicidal activity of caged compounds and 4-(hydroxymethyl)-7-substituted coumarins was studied against Vigna radiata . The new formulation provided greater control over the release of 2,4-D by UV-vis light and also demonstrated the potential of the PRPGs not only to act as a delivery device but also to possess herbicidal activity after photorelease.     

Spatial variability of 2,4-dichlorophenoxyacetic acid (2,4-D) mineralisation potential at a millimetre scale in soil

We analysed the ability of soil units of millimetre size to mineralise a herbicide, 2,4-D, using incubations of individual aggregates (2-7 mm diameter) and 6×6×6 mm³ cubes dissected from soil cores, under standard conditions. Mineralisation of ¹⁴C-ring labelled 2,4-D was measured using a barite paper trap and a Phosphorimager to record the evolved ¹⁴C-CO₂ from these very small soil samples. We found a large variability of 2,4-D mineralisation potential between aggregate size classes, between individual aggregates of the same size and between the different dissected cubes from a given core. We explained this variability by an uneven distribution of the degrading microorganisms at this scale, and to a lesser extent, an uneven distribution of C, necessary for co-metabolism. Furthermore, we found that in a soil core, the dissected cubes with a large mineralisation potential were not randomly distributed, but rather organised into centimetre sized hot spots.     

Kinetic modeling of 2,4-dichlorophenoxyacetic acid (2,4-D) degradation in soil slurry by anodic fenton treatment

Anodic Fenton treatment (AFT) has been shown to be a promising technology in pesticide wastewater treatment. However, no research has been conducted on the AFT application to contaminated soils. In this study, the 2,4-D degradation kinetics of AFT in a silt loam soil slurry were investigated for the first time, and the effects of various experimental conditions including initial 2,4-D concentration, Fenton reagent delivery rate, amount of humic acid (HA) addition, and pH were examined. The 2,4-D degradation in soil slurry by AFT was found to follow a two-stage kinetic model. During the early stage of AFT (the first 4-5 min), the 2,4-D concentration profile followed a pseudo-first-order kinetic model. In the later stage (typically after 5 or 6 min), the AFT kinetic model provided a better fit. This result is most likely due to the existence of (*)OH scavengers and 2,4-D sorption on soil. The Fe(2+) delivery rate was shown to be a more significant factor in degradation rate than the H(2)O(2) delivery rate when the Fe(2+)/H(2)O(2) ratios were in the range of 1:2 to 1:10. The presence of HA in soil lowered the AFT rate, most probably due to the competition with 2,4-D for consumption of (*)OH and increased sorption of 2,4-D on soil. The optimal pH for 2,4-D degradation in soil slurry by AFT was observed to be in the range of pH 2-3.     

Microbial mineralization of atrazine and 2,4-dichlorophenoxyacetic acid in riparian pasture and forest soils

Microbial biomass and mineralization of atrazine [2-chloro-4(ethylamino)-6(isopropylamino)s-triazine] and 2,4-D (2,4-dichlorphenoxyacetic acid) were examined in the top 10 cm of riparian pasture soils and in the litter layer and top 10 cm of mineral soils of riparian forest ecosystems. The riparian forest litter had higher levels of active and total fungal biomass than forest or pasture mineral soils in winter, spring, and fall. Active bacterial biomass was higher in forest litter than in forest and pasture mineral soils in spring and autumn, and higher in forest mineral soils than in pasture soils in summer. Total bacterial biomass was higher in forest mineral soils than in pasture soils during all seasons. In spring, it was also higher in forest litter than in pasture soils. Atrazie and 2,4-D mineralization in pasture soils was exceeded by that in forest litter in spring and autumn and by that in forest mineral soils in summer and autumn. There was no correlation between either active or total fungal and bacterial biomass with pesticide degradation.     

The influence of nitrogen on atrazine and 2,4-dichlorophenoxyacetic acid mineralization in grassland soils

The influence of fertilizer N on the mineralization of atrazine [2-chloro-4(ethylamino)-6(isopropylamino)-s-triazine] and 2,4-D (2,4-dichlorophenoxyacetic acid) in soils was assessed in microcosms using radiometric techniques. N equivalent to 0, 250, and 500 kg N as NH₄NO₃ ha^-1 was added to three grassland soils. Compared to the control, the 250- and 500-kg treatments suppressed mineralization of atrazine by 75 and 54%, respectively, and inhibited mineralization of 2,4-D by 89 and 30%, respectively. Active fungal biomass responded to the N treatments in an opposite manner to herbicide mineralization. Compared to the control, the 250- and 500-kg treatments increased the active fungal biomass by more than 300 and 30%, respectively. These results agree with other observations that N can suppress the decomposition of resistant compounds but stimulate the primary growth of fungi. The degree of suppression was not related to the amount of N added nor to the inherent soil N levels before treatment. The interaction between the N additions and the active fungal biomass in affecting herbicide mineralization suggests that N may alter microbial processes and their use of C sources and thus influence rates of herbicide degradation in the field.     

Uniformly (14)C-ring-labeled 2,4-dichlorophenoxyacetic acid: a metabolism study in bluegill sunfish, Lepomis macrochirus.

The fate of 2,4-dichlorophenoxyacetic acid (2,4-D), a mixture of [phenyl(U)-(14)C]-2,4-D and unlabeled 2,4-D, in bluegill sunfish was investigated after exposure to approximately 11 ppm under static conditions for 4 days. Total radioactive residues (TRR) in whole fish increased from 0.41 ppm on day 1 to 0.60 ppm on day 3. TRR levels in fillet (edible) and viscera (nonedible) of treated fish on day 4 were 0.41 and 1.9 ppm, respectively. Most residues in both matrices were acetonitrile soluble; small amounts were hexane soluble or unextractable with solvents. Acid and base hydrolyses with ethyl acetate partitioning were used to release the fillet unextractable residues. The identification of 2,4-D and 2,4-dichlorophenol (2,4-DCP) in the fillet was conclusively confirmed by GC-MS analysis. On the basis of the experimental data from this study, a metabolic pathway for 2,4-D in bluegill sunfish in which the 2,4-D is metabolized to 2,4-DCP and conjugates of 2,4-D and 2,4-DCP is proposed.     

Interaction of the 2,4-dichlorophenoxyacetic acid herbicide with soil organic matter moieties: a theoretical study

The determination of the structure of humic substances from soils and natural waters is an intriguing problem in soil science. Humic substances consist of molecules covering a broad distribution of molecular size and involving different functional groups. Taking this into account, we have chosen smaller model systems with functional groups typically present in humic substances. We investigated theoretically, by quantum chemical calculations, the environmental effects on the complexes formed from the interaction of 2,4‐dichlorophenoxyacetic acid and its anion with acetaldehyde, methanol, methylamine, protonated methylamine, acetic acid and water. The important case of a cation bridge mechanism, with Ca²⁺ as the bridging cation, is also included into the set of model reactions. It is found that this cation bridge belongs to one of the most stable mechanisms of fixation of organic compounds in soils. According to our calculations the hydroxyl group forms the most stable complexes with 2,4‐D in a polar solvent environment.