Relationships between microbial biomass and dissipation of 2,4-D and dicamba in soil

A study was conducted to evaluate relationships between microbial biomass and the dissipation of 2,4-D (2,4-dichlorophenoxy acetic acid) and dicamba (2-methoxy-3,6-dichlorobenzoic acid) in soil. We hypothesized that the size of the microbial biomass should be a strong predictor of the pesticide degradation capacity of a particular soil. Soils with a high microbial biomass should have relatively high levels of general microbial activity and should support a diversity of degradation pathways. In this study, we quantified the degradation of 2,4-D and dicamba in a range of soils with different concentrations of microbial biomass. The herbicides 2,4-D and dicamba were added to similar soils collected from five different land use types (home lawn, cornfield, upland hardwood forest, wetland forest, and aquifer material) and incubated for 80 days under laboratory conditions. Herbicide residue and microbial biomass (C and N) analyses were performed 5, 10, 20, 40, and 80 days following herbicide application. Microbial biomass-C and -N and soil organic matter content were positively correlated with dissipation of 2,4-D and dicamba. The results suggest that there are relationships between the size of the soil microbial biomass and the herbicide degradation capacity of an ecosystem. These relationships may be useful for developing approaches for evaluating and predicting the fate of pesticides in different ecosystems.     

Relationships between microbial biomass and dissipation of 2,4-D and dicamba in soil

A study was conducted to evaluate relationships between microbial biomass and the dissipation of 2,4-D (2,4-dichlorophenoxy acetic acid) and dicamba (2-methoxy-3,6-dichlorobenzoic acid) in soil. We hypothesized that the size of the microbial biomass should be a strong predictor of the pesticide degradation capacity of a particular soil. Soils with a high microbial biomass should have relatively high levels of general microbial activity and should support a diversity of degradation pathways. In this study, we quantified the degradation of 2,4-D and dicamba in a range of soils with different concentrations of microbial biomass. The herbicides 2,4-D and dicamba were added to similar soils collected from five different land use types (home lawn, cornfield, upland hardwood forest, wetland forest, and aquifer material) and incubated for 80 days under laboratory conditions. Herbicide residue and microbial biomass (C and N) analyses were performed 5, 10, 20, 40, and 80 days following herbicide application. Microbial biomass-C and -N and soil organic matter content were positively correlated with dissipation of 2,4-D and dicamba. The results suggest that there are relationships between the size of the soil microbial biomass and the herbicide degradation capacity of an ecosystem. These relationships may be useful for developing approaches for evaluating and predicting the fate of pesticides in different ecosystems.     

Extractability of 2,4-D,Dicamba and MCPP from Soil

The adsorption of herbicides on soil colloids is a major factor determining their mobility, persistence, and activity in soils. Solvent extraction could be a viable option for removing sorbed contaminants in soils. This study evaluated the extractability of three herbicides: 2,4 dichlorophenoxy-acetic acid (2,4-D), 4-chloro-2-methylphenoxypropanoic acid (mecoprop acid or MCPP), and 3,6-dichloro-2-methoxybenzoic acid (dicamba). Three solvents (water, methanol, and iso-propanol) and three methods of extraction (column, batch, and soxhlet) were compared for their efficiencies in removing the herbicides from three soils (loamy sand, silt loam, and silty clay). Both linear and non-linear Freundlich isotherms were used to predict sorption intensity of herbicides on soils subjected to various extraction methods and conditions. High K_dand K_fr, and low N values were obtained for all herbicides in silty clay soil by batch extraction. Methanol was the best solvent removing approximately 97% of all added herbicides from the loamy sand either by column or soxhlet extraction method. Isopropanol ranked second by removing over 90% of all herbicides by soxhelet extraction from all three soils. However, water was ineffective in removing herbicides from any of the soils using any of the three extracting procedures used in this study. In general, the extent of herbicide removal depended on soil type, herbicide concentration, extraction procedure, solvent type and amount, and extraction time.     

Electron capture gas-liquid chromatographic method for the simultaneous analysis of 2,4-D, dicamba, and mecoprop residues in soil, wheat, and barley.

A method has been developed for the simultaneous analysis of 2,4-D (2,4-dichlorophenoxy-acetic acid), dicamba (2-methoxy-3,6-dichloro-benzoic acid), and mecoprop (MCPP; 2-[(4-chloro-o-tolyl) oxy] propionic acid) residues in soil, wheat, and barley. Soil and crop samples are extracted with acidic acetone and methanol, respectively. The extracts in diethyl ether are esterified with diazomethane and cleaned up by passing through a Florisil column. Extracts are analyzed by gas-liquid chromatography, using an electron capture detector to determine 2,4-D and dicamba residues. Mecoprop in the extract is not detected at low levels of concentration. However, bromination of the extract increases the response of the electron capture detector to mecoprop. The method is sensitive to about 0.05 ppm 2,4-D and dicamba and 0.5 ppm mecoprop. Recoveries of these 3 herbicides added to soil, wheat, and barley samples at 0.05, 0.1, 0.5, and 1.0 ppm levels were between 65 and 93%. The method was used for the simultaneous analysis of 2,4-D, dicamba, and mecoprop residues in wheat, barley, and soil samples obtained from fields sprayed with the herbicide formulation Kil-Mor.     

2,4-D丁酯的水解与光解特性研究

通过室内模拟试验,研究2,4-D丁酯在不同pH值和温度下的水解动态和在有机溶剂中的光解特性。结果表明,2,4-D丁酯的水解与光解均符合一级动力学方程。在pH7以下的缓冲溶液中,2,4-D丁酯的水解反应十分缓慢,但在碱性溶液中其水解速率加快。25℃下2,4-D丁酯在pH5、7和9的缓冲溶液中的水解半衰期分别为23.5、5.8d和10.7min。2,4-D丁酯的水解速率随温度升高而增加,在温度为15、25℃和35℃的pH7缓冲溶液中的水解半衰期分别为21.5、5.8、3.9d,平均温度效应系数为2.57。2,4-D丁酯水解反应的活化能与温度之间无明显相关性,而活化熵与温度呈显著相关性。2,4-D丁酯的水解主要由活化熵所驱动。采用GC-MS技术对2,4-D丁酯水解产物进行鉴定,确定水解产物主要是2,4-二氯苯氧乙酸和2,4-二氯苯酚。2,4-D丁酯在正己烷中光解速率比在甲醇中快,在丙酮中几乎不发生光解,其光解速率随浓度的升高而减慢。     

The millimetre-scale distribution of 2,4-D and its degraders drives the fate of 2,4-D at the soil core scale

The biodegradation of organic compounds in soil is a key process that has major implications for different ecosystem services such as soil fertility, air and water quality, and climate regulation. Due to the complexity of soil, the distributions of organic compounds and microorganisms are heterogeneous on sub-cm scales, and biodegradation is therefore partly controlled by the respective localizations of organic substrates and degraders. If they are not co-localized, transfer processes become crucial for the accessibility and availability of the substrate to degraders. This spatial interaction is still poorly understood, leading to poor predictions of organic compound dynamics in soils. The objectives of this work were to better understand how the mm-scale distribution of a model pesticide, 2,4-dichlorophenoxyacetic acid (2,4-D), and its degraders drives the fate of 2,4-D at the cm soil core scale. We constructed cm-scale soil cores combining sterilized and “natural” soil aggregates in which we controlled the initial distributions of 2,4-D and soil microorganisms with the following spatial distributions: i) a homogeneous distribution of microorganisms and 2,4-D at the core-scale, ii) a co-localized distribution of microorganisms and 2,4-D in a single spot (360 mm³) and iii) a disjoint localization of microorganisms and 2,4-D in 2 soil spots (360 mm³) separated by 2 cm. Two sets of experiments were performed: one used radiolabeled ¹⁴C-2,4-D to study the fate of 2,4-D, and the other used ¹²C-2,4-D to follow the dynamics of degraders. Microcosms were incubated at 20 °C and at field capacity (−31.6 kPa). At the core scale, we followed 2,4-D mineralization over time. On three dates, soil cores with microorganisms and 2,4-D localized in soil spots, were cut out in slices and then in 360 mm³ soil cubes. The individual soil cubes were then independently analysed for extractable and non-extractable ¹⁴C and for degraders (quantitative PCR of tfdA genes). Knowing the initial position of each soil cube allowed us to establish 3D maps of 2,4-D residues and degraders in soil. The results indicated that microorganisms and pesticide localizations in soil are major driving factors of i) pesticide biodegradation, by regulating the accessibility of 2,4-D to degrading microorganisms (by diffusion); and ii) the formation of non-extractable residues (NER). These results also emphasized the dominant role of microorganisms in the formation and localization of biogenic NER at a mm-scale. To conclude, these results demonstrate the importance of considering micro-scale processes to better understand the fate of pesticides and more generally of soil organic substrates at upper scales in soil and suggest that such spatial heterogeneity should not be neglected when predicting the fate of organic compounds in soils.     

2，4-二氯苯氧基乙酸在土壤中的吸附淋溶特性

农药在土壤中的吸附和淋溶特性是评价其环境行为的重要指标,特别是决定了其在土壤中的迁移性。本文分别利用振荡平衡法和柱淋溶法研究了2,4-二氯苯氧基乙酸（2,4-D）在不同土壤中的吸附和淋溶特性及其影响因素。结果表明,2,4-D在3种供试土壤上的吸附特性能较好地用线性吸附等温线拟合,吸附常数心在0．95-1．54L·kg^-1之间,很难被土壤吸附。影响2,4-D在土壤中吸附的因素主要是土壤pH值,其次是有机质含量。土壤pH值增高,离子态的2,4-D量增加,吸附减弱;2,4-D在土壤中具有较强的淋溶性,影响其淋溶性能的主要因素是土壤pH值,pH值越高,淋溶性能越强。     

Fate of 14C-ring-labeled 2,4-D, 2,4-dichlorophenol and 4-chlorophenol during straw composting

Experiments were carried out to study the transformation of ¹⁴C-ring-labeled 2,4-D and the two related chlorophenols 4-chlorophenol (4-CP) and 2,4-dichlorophenol (4-DCP) during straw composting under controlled laboratory conditions. Incubation under sterile and nonsterile conditions was done to evaluate the relative importance of the biotic and abiotic processes. Pre-composted straw was treated with the three chemicals. The availability of the different chemicals was monitored during incubations as well as their degradation. Under nonsterile conditions, the mineralization of both chlorophenols reached 20% of the applied compounds, whereas it was 52% for 2,4-D. Transitory water-soluble metabolites of 2,4-D and chlorophenols were formed but they disappeared rapidly. After 21 days, 21% of the 2,4-D and 38% of the 2,4-DCP was stabilized as nonextractable (bound) residues under nonsterile conditions. Bound residues of both chemicals were negligible under sterile conditions. Availability of chemicals as estimated by water extraction decreased during incubation proportionally to mineralization and to the formation of bound residues. The increase in immobilization of the chemical residues was stronger under nonsterile conditions than under sterile conditions. Under nonsterile conditions 71% of the 4-CP was recovered as bound residues, whereas under sterile conditions 30% of the applied 4-CP formed bound residues after formaldehyde addition and only 8% with autoclaved straw. Global microbial activity decreased in the presence of the chlorophenols probably due to their toxic effect. These data indicate that the biological activity associated with straw transformation during composting stimulates the depletion of 2,4-D and chlorophenols by mineralization and by formation of bound residues. Received: 6 September 1996     

Sorption Studies of 2,4-D on Selected Soils

Adsorption/desorption characteristics of the herbicide 2,4-D on various types of soils were investigated. Batch equilibrium techniques were used in the laboratory experiments. Data were fitted to the linear and Freundlich sorption equations. K and Kf values ranged between 0.32–1.89 L- 1 mg and 2.6 × 10-3 – 7.4 mg kg- 1, respectively. Results showed that both for linear and Freundlich adsorption equations, for all soils, K and Kf were correlated to the organic matter content (r = 0.87 and r = 0.66, respectively). Adsorption was also positively correlated with silt and clay content of soils (r = 0.53) and negatively correlated with sand content.     

Dissipation of 2,4-D glyphosate and paraquat in river water

Dissipation of herbicides in river water was determined by adding different concentrations of 2,4-D, glyphosate and paraquat to samples of river water. A small variation of dissipation of radioactivity for¹⁴C-2,4-D in higher and lower concentrations and in different samples of river water was found. But about half the radioactivity disappeared from water samples of original glyphosate concentration at 100 mg L^?1 and, in the case of 100 μg L^?1, only 11 to 22% remained in the samples of river water after 56 d incubation except the sample from Hsin-Tien River. More than 80% of paraquat remained in water samples. Determination of octanol-water partition coefficient (Kow) showed a large difference in amounts of 2,4-D partitioned in water phase at different pH values, 97.4% at the higher pH of ionic state and 5.2% at the lower pH of molecular state, implying that pH value of water might affect the bioaccumulation process of 2,4-D. The result showed that 95.0% of glyphosate present in water phase in ionic form (higher pH) and 82.3% in molecular form (lower pH), indicating that glyphosate might have no affect on the biomagnification, since most of glyphosate could be excreted with water by organisms.     

Accumulation of 2,4-D and glyphosate in fish and water hyacinth

At a concentration of approximately one hundredth and one thousandth of the 48-hr LC₅₀ values, the accumulation of radioactivity and relative concentration of 2,4-D and glyphosate in carp and tilapia were studied by using labelled and unlabelled chemicals. About 83 (at a concentration of 0.5 ppm) and 91% (of 0.05 ppm) of the radioactive matter remained in the water until 14 days after ¹⁴C-2,4-D amended, but only 17.2% of glyphosate remained in the water with 0.05 ppm concentration of glyphosate. No significant variation was shown in the accumulation of the concentration of herbicide in fish from 2 to 7 d. Although glyphosate disappeared within 3 d in water under sunlight, the radiochemicals in the water hyacinth remained constant to the 14th d.     

ADSORPTION OF THE HERBICIDE 2,4-D ON GOETHITE

Adsorption, of the herbicide 2,4-Dichlorophenoxyacetic acid (2,4-D) on an iron oxide, goethite, was studied in aqueous suspensions as a function of solution pH, ionic strength of the medium, and initial 2,4-D concentration. The 2,4-D anion was reversibly adsorbed on positively charged goethite surfaces, maximum adsorption being observed near the pK_a of 2,4-D (2.73) and at low ionic strength. Within certain levels of adsorption (5–22 mg 2,4-D adsorbed/g goethite) the complex became hydrophobic and floated to the liquid surface. This flotation effect disappeared on further adsorption. It is suggested that adsorbed 2,4-D anions are orientated with their hydro-phobic aromatic ends directed towards the solution, the carboxyl groups being weakly bound to positive sites on the oxide surface. At high levels of adsorption, some of the anions are orientated in the opposite direction by π–π interaction, with the first adsorbed layer and the surface reverts to its hydrophilic nature.     

Bioavailability of the herbicide 2,4-D formulated with organoclays

Research on organoclays as sorbents of pesticides has shown the usefulness of these materials as pesticide supports to prolong the efficacy of soil-applied pesticides and to reduce the large transport losses that usually affect pesticides applied in an immediately available form. Nevertheless, little information exists on the availability of organoclay-formulated pesticides for bacterial degradation. In this work, laboratory experiments were conducted to determine the adsorption-desorption behavior of two hexadecyltrimethylammonium-treated Arizona montmorillonites (SA-HDTMA₅₀ and SA-HDTMA₁₀₀) for the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D), and to evaluate the ability of these organoclays to slow the release of the herbicide and to reduce herbicide leaching losses as compared to the free (technical) compound. The kinetics of mineralization of free and formulated 2,4-D by adapted bacteria was also determined. Organoclay-based formulations of 2,4-D displayed slow release properties in water and reduced herbicide leaching through soil columns, while maintained a herbicidal efficacy similar to that of the free (technical) 2,4-D. The total amount of ¹⁴C-2,4-D mineralized at the end of the biodegradation experiment (t=130 h) ranged between 30% and 46% of the formulated herbicide, which represented 53-81% of the amount of free 2,4-D mineralized in the same conditions. The release, leaching, and mineralization patterns of the formulated herbicide were found to depend both on the affinity of the organoclay for the herbicide and on the degree of interaction promoted during the preparation of the herbicide-organoclay complex. This suggests the possibility to select diverse preparations to achieve the desired release, leaching and biodegradation behavior.     

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.     

苯磺隆和2,4-D胁迫对土壤微生物影响的研究

以盆栽试验研究了除草剂苯磺隆、2,4-D对石灰性褐土中土壤微生物群落的影响。结果表明,在供试浓度下,土壤微生物对两种除草剂的感应存在一定的差异性。苯磺隆高浓度处理在最初3d极显著地抑制细菌生长,之后对土壤细菌具有刺激作用,特别是培养结束时激活率还高达917.6%,低浓度处理呈极显著的刺激作用;苯磺隆对土壤放线菌具有显著的刺激作用,对土壤真菌有强烈的抑制作用,最高抑制率达100%,到培养结束时(60d)真菌数量还未恢复到对照水平。2,4-D处理对土壤放线菌具有明显的抑制、激活的波动性,对土壤细菌、真菌有强烈的抑制作用。     

Herbicide 2,4-D: A Review of Toxicity on Non-Target Organisms

The intensive use of pesticides has increased exponentially in Brazil and worldwide due to the need to meet the food demands of a growing population. If the management/monitoring of the use of pesticides is adequately performed, it would not compromise the expected benefits or have negative effects on the environment as a whole. In order to examine the information available on herbicide use in Brazil and worldwide, this paper presents a review of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) and its chemical properties, action on target organisms, environmental fate, and toxicity to non-target organisms. This herbicide is a synthetic auxin used to control broad-leaved weeds, and the action in target organisms is well known. Although 2,4-D has been widely used worldwide, many studies have shown that this herbicide induces alterations in non-target organisms. Therefore, ecotoxicology studies are important to assess the risk the herbicides can be to different ecosystems. Thus, it is advised to use this herbicide and other pesticides with caution.     

Degradation of [carboxyl-14C] 2,4-D and [ring-U-14C] 2,4-D in 114 agricultural soils as affected by soil organic carbon content

This study compared the degradation of [carboxyl-¹⁴C] 2,4-dichlorophenoxyacetic acid (2,4-D) (C2,4-D) and [ring-U-¹⁴C] 2,4-D (R2,4-D) in 114 agricultural soils (0–15 cm) as affected by 2,4-D sorption and soil properties (organic carbon content, pH, clay content, carbonate content, cation exchange capacity, total microbial activity). The sample area was confined to Alberta, Canada, located 49–60° north longitude and 110–120° west latitude and soils were grouped by soil organic carbon content (SOC) (0–0.99%, 1–1.99%, 2–2.99%, 3–3.99% and >4% SOC). Degradation rates of C2,4-D and R2,4-D followed first-order kinetics in all soils. Although total microbial activity increased with increasing SOC, degradation rates and total degradation of C2,4-D and R2,4-D decreased with increasing SOC because of increased sorption of 2,4-D by soil and reduced bioavailability of 2,4-D and its metabolites. Rates of R2,4-D degradation were more limited by sorption than rates of C2,4-D degradation, possibly because of greater sorption and formation of bound residues of 2,4-D metabolites relative to the 2,4-D parent molecule. Based on the sorption and degradation parameters quantified, there were two distinct groups of soils, those with less than 1% SOC and those with greater than 1% SOC. Specifically, soils with less than 1% SOC had, on average, 2.4 times smaller soil organic carbon sorption coefficients and 1.4 times smaller 2,4-D half-lives than soils with more than 1% SOC. In regional scale model simulations of pesticide leaching to groundwater, covering many soils, input parameters for each pesticide include a single soil organic carbon sorption coefficient and single half-life value. Our results imply, however, that the approach to these regional scale assessments could be improved by adjusting the values of these two input parameters according to SOC. Specifically, this study indicates that for 2,4-D and Alberta soils containing less than 1% SOC, the 2,4-D pesticide parameters obtained from generic databases should be divided by 2.5 (soil organic carbon sorption coefficient) and 1.5 (half-life value).