Exposure of homeowners and bystanders to 2,4-dichlorophenoxyacetic acid (2,4-D).

Total body dose received in home gardeners applying 2,4-D and bystanders living within the household, but not applying the pesticide was measured. Levels of 2,4-D were monitored in air samples both inside the home and downwind of the application site. Homeowners were divided into protective and non-protective apparel groups and applied both a granular and liquid formulation of 2,4-D on two separate dates. Analyses of urine collected from homeowners for 96 hours following applications found total body doses ranging from non-detectable to 0.0071 mg/kg of body weight. The highest exposures occurred in the non-protected group and were consistently associated with spills of the liquid concentrate or excessive contact with the dilute mixture on the hands or forearms. Residues of 2,4-D were not detected in urine samples supplied by bystanders to home applicators. Residues of 2,4-D were detected in five of the 76 air samples taken during the home applications. Two of these air samples coincided with measurable applicator exposure but it is unlikely that this was a major route of exposure.     

Concurrent 2,4-D and triclopyr biomonitoring of backpack applicators, mixer/loader and field supervisor in forestry

Two herbicides, 2,4-D and triclopyr esters (application ratio 1.6:1 acid equivalents) were applied as a tank mix by a crew of 8 backpack sprayer applicators, a mixer/loader, and a field supervisor. The crew was employed in a conifer release program in northern California during the summer of 2002. Biomonitoring (urine, 24 h) utilized 2,4-D and triclopyr (a.e.) as rapidly excreted exposure biomarkers. The absorbed dosages of 2,4-D and triclopyr were calculated based upon cotton whole body suits and biomonitoring. Dosages based upon accumulation of the herbicides on body suits averaged 42.6 μg (a.e.) 2,4-D/kg-d and 8.0 μg (a.e.) triclopyr/kg-d. Six consecutive days of concurrent urine collections showed that backpack applicators excreted an average of 11.0 μg (a.e.) 2,4-D/kg-d and 18.9 μg (a.e.) triclopyr/kg-d. Estimates based upon curve fitting were 17.1 and 29.3 μg (a.e.)/kg-d, respectively. Results suggest that passive dosimetry for 2,4-D consistently overestimated the dosage measured using biomonitoring by a factor of 2-3 fold, while for triclopyr, passive dosimetry underestimated the absorbed dose based on biomonitoring by a factor of 2-4 fold.     

Fungal bioconversion of 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4-dichlorophenol (2,4-DCP)

Ninety strains of fungi from the collection of our mycology laboratory were tested in Galzy and Slonimski (GS) synthetic liquid medium for their ability to degrade the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) and its by-product, 2,4-dichlorophenol (2,4-DCP) at 100 mg l(-1), each. Evolution of the amounts of each chemical in the culture media was monitored by HPLC. After 5 days of cultivation, the best results were obtained with Aspergillus penicilloides and Mortierella isabellina for 2,4-D and with Chrysosporium pannorum and Mucor genevensis for 2,4-DCP. The data collected seemed to prove, on one hand, that the strains responses varied with the taxonomic groups and the chemicals tested, and, on the other hand, that 2,4-D was less accessible to fungal degradation than 2,4-DCP. In each case, kinetics studies with the two most efficient strains revealed that there was a lag phase of 1 day before the onset of 2,4-D degradation, whereas there was none during 2,4-DCP degradation. Moreover, 2,4-DCP was detected transiently during 2,4-D degradation. Finally, M. isabellina improved its degradation potential in Tartaric Acid (TA) medium relative to GS and Malt Extract (ME) media.     

Determination of 2,4-dichlorophenoxyacetic acid (2,4-D) in human urine with mass selective detection.

Method development and validation studies have been completed on an assay that will allow the determination of 2,4-dichlorophenoxyacetic acid (2,4-D) in human urine. The accurate determination of 2,4-D in urine is an important factor in monitoring worker and population exposure. These studies successfully validated a method for the detection of 2,4-D in urine at a limit of quantitation (LOQ) of 5.00 ppb (parts per billion) using gas chromatography with mass selective detection (GC/MSD). The first study involved the determination of 2,4-D in control human urine and urine samples fortified with 2,4-D. Due to chromatographic interference, a second study was conducted using 14C-2,4-D to verify the recoverability of 2,4-D from human urine at low levels using the GC/MSD method. The second study supports the results of the original data. The 2,4-D was extracted from human urine using a procedure involving hydrolysis using potassium hydroxide, followed by a liquid-liquid extraction into methylene chloride. The extracted samples were derivatized with diazomethane. The methylated fraction was analyzed by GC/MSD. Quantitation was made by comparison to methylated reference standards of 2,4-D. Aliquots fortified at 5-, 50-, and 500-ppb levels were analyzed. The overall mean recovery for all fortified samples was 90.3% with a relative standard deviation of 14.31%.     

Effects of culture parameters on the degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4-dichlorophenol (2,4-DCP) by selected fungi. Groupe pour l'Etude du Devenir des Xénobiotiques dans l'Environnement (GEDEXE).

In order to enhance 2,4-D and 2,4-DCP degradation by four selected fungi (Cunninghamella elegans, C. echinulata, Rhizoctonia solani and Verticillium lecanii), three culture parameters (initial chemical concentration, amounts of glucose and nitrogen) were varied. The levels of both xenobiotics in the culture media were monitored by HPLC analysis after five days of cultivation. The best results were obtained at low initial concentration (20 mg.L-1 vs 100) and with low amounts of glucose (5 g.L-1 vs 10) and nitrogen (2.4 mM vs 24). When these two elements were lacking from the culture media, biodegradation was not suppressed, but took place to a lesser extent. Thus, initial chemical concentration and amounts of carbon and nitrogen, in the culture medium, were shown to strongly influence the extent of 2,4-D and 2,4-DCP removal by fungi.     

Dicamba and 2,4-D residues following applicator cleanout: A potential point source to the environment and worker exposure

This paper presents a survey of pesticide residues in tanks following application and throughout the cleanout procedure as conducted by 46 volunteer operators across Colorado. While many pesticides were detected, this paper focuses on dicamba and 2,4-D, which were detected by liquid chromatography/tandem mass spectroscopy (LC-MS/MS). An exponential decrease in concentration was observed with sequential rinses, although this decrease may be more rapid for more water-soluble pesticides. More than 95% of the pesticide in the prerinse solution was removed by the end of the third rinse in all but three operator samples. Concentrations after three rinses were 0.41 ± 0.25 and 3.3 ± 1.1 mg/L for dicamba and 2,4-D, respectively. These concentrations suggest that the recommended practice of three rinses may not be adequate to eliminate off-target effects or point sources of pesticide waste, and that the recommended standard of personal protective equipment is essential to prevent worker exposure to the chemicals.

Implications:?This paper demonstrates that the waste generated during cleanout of pesticide application devices constitutes a potential source of pollution and worker exposure. In particular, while the first rinse of pesticide containers is often treated as hazardous waste and reapplied to crops, the remaining rinses are not. This work demonstrates that the wastewater generated in subsequent rinses can have high enough concentrations to impact worker health, cause off-target effects on crops, and potentially constitute a point source of pesticides. The practical implication is for improved recommendations and regulations regarding pesticide applicators and their cleanout process.     

Survey of Airborne 2,4-D in South-Central Washington

The extensive application of 2,4-D herbicides to wheat and other agricultural crops in the states of Washington and Oregon can produce "off-target" damage when the 2,4-D formulations are transported by the atmosphere to sensitive crops, such as grapes. During May-June of 1973 and April-June of 1974, a 2,4-D monitoring network in south-central Washington collected samples for subsequent herbicide analysis. The daily, 24 hr field samples were collected with differential Impactor-impinger air samplers and were routinely analyzed in the analytical laboratory by electron-capture gas chromatography. In addition, gas chromatography/mass spec-trometry was employed for positive identification of the 2,4-D esters and for comparative quantitative analysis. The complete sampling and analytical methodology, the 2,4-D concentration data for 1973 and 1974, the agricultural 2,4-D application records and crop Injury reports, and the concomitant meteorological data are described in this paper.     

Fine route for an efficient removal of 2,4-dichlorophenoxyacetic acid (2,4-D) by zeolite-supported TiO2

Zeolites HY, Hbeta and HZSM-5 with different physico-chemical properties were chosen as support for TiO2 to illustrate their adsorption, dispersion and electronic structure in photocatalysis. The extent of TiO2 loading was monitored by XRD and BET surface area measurements. The adsorption capacity of HY zeolite was found to be high and hence chosen for further modification to continue the investigation. Photodegradation kinetics were carried out with 2,4-dichlorophenoxyacetic acid (2,4-D) in aqueous solution. The extent of 2,4-D degradation on TiO2/HY loading revealed the importance of adsorption in photocatalysis. Mineralisation studies on all three zeolites with 1 wt.% TiO2 loading demonstrated the good dispersion properties of TiO2/HY. Its photocatalytic activity was found to be excellent with formulated 2,4-D. Comparison of relative photonic efficiencies demonstrated that supported photocatalysts exhibited higher activity than some of the commercial photocatalysts. The high activity of supported TiO2 is due to synergistic effects of improved adsorption of 2,4-D and efficient delocalisation of photogenerated electrons by zeolite support.     

2,4-Dichlorophenoxyacetic acid (2,4-D) sorption and degradation dynamics in three agricultural soils

The fate and transport of 2,4-dichlorophenoxyacetic acid (2,4-D) in the subsurface is affected by a complex, time-dependent interplay between sorption and mineralization processes. 2,4-D is biodegradable in soils, while adsorption/desorption is influenced by both soil organic matter content and soil pH. In order to assess the dynamic interactions between sorption and mineralization, 2,4-D mineralization experiments were carried using three different soils (clay, loam and sand) assuming different contact times. Mineralization appeared to be the main process limiting 2,4-D availability, with each soil containing its own 2,4-D decomposers. For the clay and the loamy soils, 45 and 48% of the applied dose were mineralized after 10 days. By comparison, mineralization in the sandy soil proceeded initially much slower because of longer lag times. While 2,4-D residues immediately after application were readily available (>93% was extractable), the herbicide was present in a mostly unavailable state (<2% extractable) in all three soils after incubation for 60 days. We found that the total amount of bound residue decreased between 30 and 60 incubation days. Bioaccumulation may have led to reversible immobilization, with some residues later becoming more readily available again to extraction and/or mineralization.     

Human exposure to 2,4-D following controlled activities on recently sprayed turf.

Total body dose of 2,4-D was determined in 10 volunteers following exposure to sprayed turf 1 hour following application and in 10 volunteers exposed 24 hours following application. Each group of 10 volunteers was divided in half and five wore long pants, a short-sleeved shirt, socks and closed footwear. The other five wore shorts and a short-sleeved shirt and were barefoot. All volunteers were exposed to a 2 by 15 m area of turf for 1 hour during which they alternated between walking and sitting or lying on the turf surface for intervals of 5 minutes. Dislodgeable residues of 2,4-D taken during the exposure sessions showed a rapid decline from 1 hour following application (8%) to 24 hours following application (1%). No detectable residues were found in 4-day urine samples supplied by volunteers except for 3 people who were barefoot and wearing shorts and contacted the turf 1 hour following 2,4-D application. The highest dose was measured in a volunteer who removed his shirt for 30 minutes of the exposure session (426 micrograms). Exposure levels of the other two volunteers who wore the prescribed clothing were lower (153 and 103 micrograms). No detectable residues were found in urine samples supplied by volunteers exposed to sprayed turf 24 hours following application. These results indicate that at the doses measured, exposure to sprayed turf should present little risk in humans. However, people can reduce exposure to non-detectable levels by remaining off treated turf for a period of 24 hours or until after rainfall or irrigation so that dislodgeable residues and therefore potential exposure are essentially zero.     

Treatment and reuse of wastewater in pesticide 2,4-D production

Waste-water from the production of pesticide 2,4-D often contains high concentrations of 2,4-DCP and 2,6-D as the primary pollutants. Treatment of waste-water collected from a 2,4-D manufacturer was carried out using a technology combining acidification with hyper-crosslinked resin NDA-150 adsorption process. The overall process recovered 5.4 kg of 2,4-DCP and 0.6 kg of 2,6-D per cubic metre of the wastewater. The treatment reduced the concentration of 2,4-DCP in the wastewater from >6000 mg/L to <0.5 mg/L. The optimal operation parameters of adsorption and desorption were determined. The hyper-crosslinked resin adsorbent can be re-used after regeneration by NaOH aqueous solution. The recovered 2,4-DCP with a sufficiently high purity may be re-used in the production of 2,4-D. The technology may thus be applied to the treatment of waste-water for reclamation of chemicals for 2,4-D production while minimising the environmental nuisances and hazards that may be caused by these chemicals.     

Chlorinated pesticides (2,4-D and DDT) biodegradation at high concentrations using immobilized Pseudomonas fluorescens

Degradation of two chlorinated pesticides (2,4-D and DDT) using a 54-mL glass column packed with tezontle (a low-cost basaltic scoria) was tested. Bacteria were cultured in YPG (yeast, peptone, and glucose) liquid medium at 32 degrees C. The rich medium was pumped during 24 h through the column to inoculate it. Later, the wasted medium was discharged and the pesticide added. Optical densities, TOC, and pesticide concentration were determined. Pesticide removals for 2,4-D (with initial concentration between 100 and 500 mg/L) were about 99%. DDT removal (at initial concentration of up to 150 mg/L) was as high as 55-99%. TOC removals for 2,4-D was in the 36-87% interval, whereas for DDT they were as high as 36-78%.     

2,4-Dichlorophenoxy acetic acid mineralization in amended soil

The application of municipal biosolid or liquid hog manure to agricultural soils under laboratory conditions at 20 degrees C influenced the fate of the herbicide 2,4-D [2,4-(dichlorophenoxy)acetic acid] in soil. When 2,4-D was added to soil at agronomic rates immediately after the addition of manure or biosolids to a coarse-textured soil, the percentage of 2,4-D mineralized at 100 days was about 47% for both treatments, compared to only 31% for control soils without amendments. The enhanced 2,4-D mineralization as a result of amendment addition was due to an increased heterotrophic microbial activity, with the greatest increases in soil respiration occurring for soils amended with biosolids. When additions of 2,4-D were delayed for one, two, or four weeks after the amendments were applied, the additions of amendments generally reduced 2,4-D mineralization in soil, particularly for manure, indicating that the effect of amendments on enhancing soil microbial activities diminished over time. In contrast, the mineralization of 2,4-D in control soils was less dependent on when 2,4-D was applied in relation to pre-incubations of soil for zero, one, two, or four weeks. The effect of manure on decreasing 2,4-D mineralization in specific soils was as large as the effect of soil texture on differences in 2,4-D mineralization across soils. Because manure was not found to impact 2,4-D sorption by soil, it is possible that 2,4-D mineralization decreased because 2,4-D transformation products were strongly sorbed onto organic carbon constituents in manure-amended soils and were therefore less accessible to microorganisms. Alternatively, microorganisms were less likely to metabolize the herbicide because they preferentially consumed the type of organic carbon in manure that is a weak sorbent for 2,4-D.     

2,4-Dichlorophenoxy Acetic Acid Mineralization in Amended Soil

The application of municipal biosolid or liquid hog manure to agricultural soils under laboratory conditions at 20°C influenced the fate of the herbicide 2,4-D [2,4-(dichlorophenoxy)acetic acid] in soil. When 2,4-D was added to soil at agronomic rates immediately after the addition of manure or biosolids to a coarse-textured soil, the percentage of 2,4-D mineralized at 100 days was about 47% for both treatments, compared to only 31% for control soils without amendments. The enhanced 2,4-D mineralization as a result of amendment addition was due to an increased heterotrophic microbial activity, with the greatest increases in soil respiration occurring for soils amended with biosolids. When additions of 2,4-D were delayed for one, two, or four weeks after the amendments were applied, the additions of amendments generally reduced 2,4-D mineralization in soil, particularly for manure, indicating that the effect of amendments on enhancing soil microbial activities diminished over time. In contrast, the mineralization of 2,4-D in control soils was less dependent on when 2,4-D was applied in relation to pre-incubations of soil for zero, one, two, or four weeks. The effect of manure on decreasing 2,4-D mineralization in specific soils was as large as the effect of soil texture on differences in 2,4-D mineralization across soils. Because manure was not found to impact 2,4-D sorption by soil, it is possible that 2,4-D mineralization decreased because 2,4-D transformation products were strongly sorbed onto organic carbon constituents in manure-amended soils and were therefore less accessible to microorganisms. Alternatively, microorganisms were less likely to metabolize the herbicide because they preferentially consumed the type of organic carbon in manure that is a weak sorbent for 2,4-D.     

Chlorinated Pesticides (2,4-D and DDT) Biodegradation at High Concentrations Using Immobilized Pseudomonas Fluorescens

Abstract

Degradation of two chlorinated pesticides (2,4-D and DDT) using a 54-mL glass column packed with tezontle (a low-cost basaltic scoria) was tested. Bacteria were cultured in YPG (yeast, peptone, and glucose) liquid medium at 32°C. The rich medium was pumped during 24 h through the column to inoculate it. Later, the wasted medium was discharged and the pesticide added. Optical densities, TOC, and pesticide concentration were determined. Pesticide removals for 2,4-D (with initial concentration between 100 and 500 mg/L) were about 99%. DDT removal (at initial concentration of up to 150 mg/L) was as high as 55–99%. TOC removals for 2,4-D was in the 36-87% interval, whereas for DDT they were as high as 36–78%.     

Light regime, riboflavin, and pH effects on 2,4-D photodegradation in water

A laboratory study was conducted to determine the effects of light regime, riboflavin, and pH on photodegradation of 2,4-D in aqueous solution. In controlled-environment chamber experiments, riboflavin sensitized 2,4-D photolysis in a concentration-dependent manner under both attenuated UV (-UV) and enhanced UV (+UV) light regimes. The photolysis half-life of 2,4-D in solutions containing 10 mg L-1 riboflavin was 9.7 and 12.5 h when exposed to +UV and -UV, respectively, compared to no photolysis in the absence of riboflavin. In contrast, the extrapolated half-life of 2,4-D in solutions containing 2.5 mg L-1 riboflavin was 46 h under +UV and 72 h under -UV. The rate of 2,4-D photolysis in the presence of riboflavin increased under both light regimes as initial pH of the solution was decreased from 7.5 to 4.5. The half-life of 2,4-D in the presence of 10 mg L-1 riboflavin at pH 4.5 and exposed to +UV was 1.6 h. Lumichrome, a principal photoproduct of riboflavin, did not photosensitize 2,4-D. Concentrations of 2,4-dichlorophenol formed as a result of riboflavin-sensitized 2,4-D photolysis were higher under the -UV than the +UV regime. These results indicate that riboflavin concentration, solution pH, and light regime are interacting factors that may be manipulated to enhance rates of aqueous 2,4-D photolysis.     

Adsorption characteristics of 2,4-dichlorophenoxyacetic acid (2,4-D) from aqueous solution on powdered activated carbon

The removal of 2,4-dichlorophenoxyacetic acid (2,4-D), one of the most commonly used phenoxy acid herbicides, from aqueous solution was studied by using acid-washed powdered activated carbon (PAC) as an adsorbent in a batch system. Adsorption equilibrium, kinetics, and thermodynamics were investigated as a function of initial pH, temperature, and initial 2,4-D concentration. Powdered activated carbon exhibited the highest 2,4-D uptake capacity of 333.3 mg g(-1) at 25 degrees C and an initial pH value of 2.0. Freundlich, Langmuir, and Redlich-Peterson isotherm models were used to express the equilibrium data of 2,4-D depending on temperature. Equilibrium data fitted very well to the Freundlich equilibrium model in the studied concentration range of 2,4-D at all the temperatures studied. Three simplified models including pseudo-first-order, pseudo-second-order, and saturation-type kinetic models were used to test the adsorption kinetics. It was shown that the adsorption of 2,4-D on PAC at 25, 35, and 45 degrees C could be best fitted by the saturation-type kinetic model with film and intraparticle diffusions being the essential rate-controlling steps. The activation energy of adsorption (EA) was determined as--1.69 kJ mole(-1). Using the thermodynamic equilibrium coefficients obtained at different temperatures, the thermodynamic constants of adsorption (deltaG degrees, deltaH degrees, and deltaS degrees) were also evaluated.     

Reductive transformation of 2,4-dichlorophenoxyacetic acid by nanoscale and microscale Fe3O4 particles

Reductive transformation of 2,4-dichlorophenoxyacetic acid (2,4-D) by nanoscale and microscale Fe₃O₄ was investigated and compared. Disappearance of the parent species and formation of reaction intermediates and products were kinetically analyzed. Results suggest that the transformation of 2,4-D followed a primary pathway of its complete reduction to phenol and a secondary pathway of sequential reductive hydrogenolysis to 2,4-dichlorophenol (2,4-DCP), chlorophenol (2-CP, 4-CP) and phenol. About 65% of 2,4-D with initial concentration of 50 μ M was transformed within 48 h in the presence of 300 mg L^?1 nanoscale Fe₃O₄, and the reaction rates increased with increasing dosage of nanoscale Fe₃O₄. The decomposition of 2,4-D proceeded rapidly at optimum pH 3.0. Chloride was identified as a reduction product for 2,4-D in the magnetite–water system. Reductive transformation of 2,4-D by microscale Fe₃O₄ was slower than that by nanoscale Fe₃O₄. The reactions apparently followed pseudo-first-order kinetics with respect to the 2,4-D transformation. The degradation rate of 2,4-D decreased with the increase of initial 2,4-D concentration. In addition, anions had a significant adverse impact on the degradation efficiency of 2,4-D.     

Effects of 2,4-D, glyphosate and paraquat on growth, photosynthesis and chlorophyll-a synthesis of Scenedesmus quadricauda Berb 614

The effects of 2,4-D, glyphosate and paraquat on growth, photosynthesis and chlorophyll-a synthesis by a freshwater green alga, Scenedesmus quadricauda Berb 614, were determined. These herbicides are the most often used in Hong Kong. Within the concentration range 0.02-200 mg/l, paraquat was more toxic than glyphosate and 2,4-D to the growth, photosynthesis and chlorophyll-a synthesis. The presence of 0.02, 0.2 or 2 mg/l of 2,4-D was not toxic to the alga. Algal growth, photosynthesis and chlorophyll-a synthesis were stimulated by the presence of low concentrations (0.02 or 0.2 and 0.02 mg/l, respectively) of 2,4-D and glyphosate. The presence of 0.02 or 0.2 mg/l of paraquat, 2 mg/l of glyphosate or 20 mg/l of 2,4-D was significantly inhibitory to the three test parameters, whereas the presence of 2 or more mg/l of paraquat, 20 or more mg/l of glyphosate or 200 mg/l of 2,4-D completely inhibited algal growth, photosynthesis and chlorophyll-a synthesis. The use of the alga as a bio-indicator of herbicide contamination in freshwater environment was discussed.     

Effects of 2,4-dichlorophenoxyacetic acid formulation on medulla spinalis of Poecilia reticulata: A histopathological study

This study investigated the possible effects of a commonly used foliar herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) formulation on medulla spinalis of lebistes. Fish were exposed to 2,4-D (15, 30, 45 mg L⁻¹), behavioral changes were monitored. Fish were fixed, histopathological examination was carried out on sections taken from the upper parts of the fish body. Histopathology showed increase in neuronal loss, swelling indicating formation of intracellular edema, vacuolization noticed as the formation of vacuoles within or adjacent to cells, deformation in the Nissl granules, pyknosis and gliosis in medulla spinalis. Behavioral changes were decreased general activity, grouping, shortness in breath, sudden rotations and jumping, loss of equilibrium and colour. In conclusion, this commercial formulation of 2,4-D is considerably neurotoxic to lebistes. Fish constitute the last link in the chain of the feeding cycle in aquatic eco-system, number of studies investigating acute and chronic neurotoxicity of various herbicides in fish should be increased.